Substituted pyrazole derivatives and their use as herbicides

ABSTRACT

New substituted pyrazole derivatives of general formula I are described ##STR1## in which R 1 , R 2 , R 3 , R 4 , R 5  and R 6  have the meanings given in the description , processes for their preparation, as well as intermediates, and their use as herbicides.

This application is a 371 of PCT/EP93/0281 filed Oct. 11, 1993.

FIELD OF THE INVENTION

This invention relates to new substituted pyrazole derivatives, theirpreparation, as well as intermediates, and their use as herbicides.

PRIOR ART

It is known that 1-phenylpyrazoles possess herbicidal activity (EP154115).

However the herbicidal activity of these compounds in not high enough orselectivity problems can occur in important crops.

The object of the present invention is to make new compounds that haveimproved biological properties over the known compounds.

It has now been found that substituted pyrazole derivatives of generalformula I ##STR2## in which

R¹ is C₁ -C₄ -alkyl;

R² is C₁ -C₄ -alkyl, C₁ -C₄ -alkylthio, C₁ -C₄ -alkoxy, each of which isoptionally substituted by one or more halogen atoms, or

R¹ and R² together form the group --(CH₂)_(m) ;

R³ is hydrogen or halogen,

R⁴ is hydrogen or C₁ -C₄ -alkyl,

R⁵ is hydrogen, nitro, cyano or the groups --COOR⁷, --C(═X)NR⁸ R⁹ or--C(═X)R¹⁰,

R⁶ is hydrogen, halogen, cyano, C₁ -C₄ -alkyl, (optionally substitutedby one or more halogen or hydroxy groups), C₁ -C₄ -alkoxy, phenyl,(optionally substituted by one or more halogen, nitro, cyano, C₁ -C₄-alkyl, C₁ -C₄ -alkoxy or halo-C₁ -C₄ -alkyl groups), pyrrolyl, or is aC₂ -C₈ -alkyl, C₃ -C₈ -alkenyl, C₃ -C₈ -alkynyl or C₃ -C₈ -alkoxy group,each of which is interrupted by one or more oxygen atoms, or is thegroup; NR¹¹ R¹² ; ##STR3##

R⁷, R⁸ and R⁹, which may be the same or different, are hydrogen or C₁-C₄ -alkyl or

R⁸ and R⁹ together with the nitrogen to which they are attached form a 5or 6 membered saturated carbocyclic ring;

R¹⁰ is hydrogen or C₁ -C₄ -alkyl, optionally substituted by one or morehalogen atoms,

R¹¹ is hydrogen, C₁ -C₄ -alkyl, C₂ -C₆ -alkenyl, C₃ -C₆ -alkynyl orphenyl (each of which is optionally substituted by one or more halogenatoms), C₃ -C₈ -cycloalkyl, cyanomethyl or the group R²¹ CO--;

R¹² is C₁ -C₆ -alkyl, C₂ -C₆ -alkenyl, C₃ -C₆ -alkynyl or phenyl (eachof which is optionally substituted by one or more halogen atoms), C₃ -C₈-cycloalkyl, cyanomethyl, C₁ -C₄ -alkoxy-C₁ -C₆ -alkyl, di-C₁ -C₄-alkylamino-C₁ -C₄ -alkyl, tetrahydrofurfurylmethyl, C₃ -C₆-alkynyl-oxy-C₁ -C₄ -alkyl, benzyl, (optionally substituted by one ormore halogen, nitro, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or halo-C₁ -C₄-alkyl groups), or is the group --C(═X)R²¹, --(CH₂)_(a) --(O)_(d) --R²⁸,--(CH₂)_(a) --O--(CH₂)_(b-) R²⁸ or --(CH₂)_(a) --X--R³⁴, and when R⁵ is--C(═O)R¹⁰, and/or when R¹ is C₁ -C₄ -alkyl, R² is difluoromethoxy, R³is bromo and R⁵ is nitro or cyano, R¹² can also be hydrogen; or

R¹¹ and R¹² together with the nitrogen to which they are attached form a3, 5 or 6 membered saturated carbocyclic or aromatic ring, in which acarbon atom is optionally substituted by an oxygen atom;

R¹³ is hydrogen, C₁ -C₄ -alkyl, C₂ -C₆ -alkenyl or C₃ -C₆ -alkynyl; orR¹³ and R¹⁴ together form the group --(CH₂)_(p) ;

R¹⁴ and R¹⁵, which may be the same or different, are C₁ -C₄ -alkyl, C₂-C₆ -alkenyl, C₃ -C₆ -alkynyl or phenyl (each of which is optionallysubstituted by one or more halogen atoms), hydrogen, C₃ -C₆ -cycloalkylor the groups --XR¹⁸ or --NR¹⁹ R²⁰ ;

R¹⁶ is hydrogen, C₁ -C₆ -alkyl, C₂ -C₆ -alkenyl, C₃ -C₆ -alkynyl, C₁ -C₄-alkylcarbonyl, cyano-C₁ -C₃ -alkyl, C₁ -C₄ -alkoxycarbonyl-C₁ -C₄-alkyl, di-C₁ -C₄ -alkoxy-carbonyl-C₁ -C₄ -alkyl, benzyl, C₁ -C₄-alkoxy-C₃ -C₈ -alkynyl, or the group --(CH₂)_(a) --R³³, --(CH₂)_(a)--X--R³⁰, --(CH₂)_(a) --X--(CH₂)_(b) --R³⁰ or --(CH₂)_(a) --X--(CH₂)_(b)--X--(CH₂)_(c) --R³⁰,

R¹⁷ is hydrogen, C₁ -C₄ -alkyl, C₂ -C₆ -alkenyl, C₃ -C₆ -alkynyl,cyano-C₁ -C₃ -alkyl, C₁ -C₄ -alkylcarbonyl-C₁ -C₃ -alkyl or phenyl,

R¹⁸ is C₁ -C₄ -alkyl, optionally substituted by one or more halogens;

R¹⁹ and R²⁰, which may be the same or different, are hydrogen or C₁ -C₄-alkyl;

R²¹ is C₁ -C₄ -alkyl, (optionally substituted by one or more halogens),C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, C₁ -C₄ -alkylthio-C ₁ -C₄ -alkyl, C₃ -C₆-cycloalkyl, phenyl, (optionally substituted by one or more halogen,nitro, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or halo-C₁ -C₄ -alkylgroups), or is the group --NR³¹ R³² or --(CH₂)_(a) --(O)_(d) --R³³ ;

R²² is C₁ -C₄ -alkoxycarbonyl or carboxy,

R²³ is chloromethyl, cyanomethyl, C₃ -C₆ -cycloalkyl (optionallyinterrupted by one or more oxygen atoms), or C₁ -C₄ -alkoxycarbonyl-C₁-C₄ -alkyl,

R²⁴ is hydroxy or the group --NR²⁵ R²⁶ ;

A is --NR²⁵ R²⁶ or --S(O)_(n) --R²⁷ ;

R²⁵ and R²⁶, which may be the same or different, are hydrogen or C₁ -C₄-alkyl;

R²⁷ is C₁ -C₄ -alkyl, C₁ -C₄ -alkoxycarbonyl-C₁ -C₄ -alkyl or carboxy,

R²⁸ is hydrogen, hydroxy, halogen, C₁ -C₄ -alkyl, (optionallysubstituted by one or more C₁ -C₄ -alkoxy groups), C₃ -C₆ -cycloalkyl(optionally interrupted by one or more oxygen atoms and optionallysubstituted by dimethyl), furyl, thienyl or --C(═O)R²⁹ ;

R²⁹ and R³⁰, which may be the same or different, are C₁ -C₄ -alkyl or C₁-C₄ -alkoxy;

R³¹ and R³², which may be the same or different, are C₁ -C₄ -alkyl orphenyl;

R³³ is C₃ -C₆ -cycloalkyl (optionally interrupted by one or more oxygenatoms and optionally substituted by dimethyl), furyl, thienyl or--C(═O)R²⁹ ;

R³⁴ is C₁ -C₄ -alkyl;

a, b and c are 1, 2 or 3;

d is 0 or 1;

m is 3 or 4;

p is 2 or 3; and

X is oxygen or sulfur, possess better herbicide properties than theknown compounds of related structure.

Particularly active are those pyrazole derivatives as defined above, inwhich

R¹ is methyl;

R² is methylthio or difluoromethoxy (and especially difluoromethoxy); or

R¹ and R² together form the group --(CH₂)₄ ;

R³ is hydrogen, chloro or bromo;

R⁴ is hydrogen;

R⁵ is hydrogen, nitro, cyano or --C(═X)R¹⁰.

In a particularly preferred group of compounds, R⁶ is hydrogen, halogen,cyano, C₁ -C₄ -alkyl, C₁₋₄ -alkylthio or --NR¹¹ R¹², with R¹¹ and R¹²preferably being hydrogen, C₁₋₄ -alkyl or C₁₋₄ -alkoxycarbonyl.

The term "halogen" means fluorine, chlorine, bromine and iodine.

It is to be understood that the term "alkyl", "alkenyl" and "alkynyl"includes branched as well as straight chained hydrocarbon groups.

The invention also includes intermediates of general formula II ##STR4##in which R¹, R² and R³ have the meanings given in general formula I,intermediates of general formula Ii ##STR5## in which R¹ and R² have themeanings given in general formula I, intermediates of general formula Ij##STR6## in which R¹, R² and R⁵ have the meanings given in generalformula I, intermediates of general formula Ik ##STR7## in which R¹, R²and R⁶ have the meanings given in general formula I, intermediates ofgeneral formula Il ##STR8## in which R¹, R² and R³ have the meaningsgiven in general formula I, and intermediates of general formula Im##STR9## in which R¹, R², R³ and R⁶ have the meanings given in generalformula I.

The compounds of the invention of general formula I can be prepared, bya process in which

A) a compound of general formula II ##STR10## in which R¹, R² and R³have the meanings given in general formula I, is reacted with a compoundof general formula III ##STR11## in which R⁴ and R⁵ have the meaningsgiven in general formula I and Y is C₁ -C₆ -alkoxy, hydroxy or halogen,or when R⁵ is hydrogen,

B) a compound of general formula II ##STR12## in which R¹, R² and R³have the meanings given in general formula I, is reacted with a2-haloacrylonitrile of formula IIIa ##STR13## or with a2,3-dihalopropionitrile of formula IIIb ##STR14## in which Hal ishalogen, or when R³ is halogen,

C) a compound of general formula Ia ##STR15## in which R¹, R², R⁵, R¹¹and R¹² have the meanings given in general formula I, is reacted firstwith a halogenating agent to give a compound of formula 1b ##STR16## inwhich R₁, R², R⁵, R¹¹ and R¹² have the meanings given in general formulaI, and Hal is halogen, and then further treated to give the desiredcompound, or when R⁵ is --C(═S)R¹⁰ and R⁶ is amino,

D) a compound of general formula Ic ##STR17## in which R¹, R², R³, R⁴and R¹⁰ have the meanings given in general formula I, is treated withLawesson's reagent, or when R³ is --OR¹⁶,

E) a compound of general formula Id ##STR18## in which R¹, R², R³, R⁴and R⁵ have the meanings given in general formula I, is first diazotisedto give a compound of formula 1e ##STR19## in which R¹, R², R³, R⁴ andR⁵ have the meanings given in general formula I, and then by heating togive a compound of formula 1f ##STR20## in which R₁, R², R³, R⁴ and R⁵have the meanings given in general formula I, which is then reacted witha compound of general formula IV

    QR.sup.16                                                  (IV)

in which R¹⁶ has the meaning given in general formula I, and Q is aleaving group, or when R⁵ is nitro and R⁶ is --SR¹⁷,

F) a compound of general formula Ig ##STR21## in which R¹, R², R³ and R⁴have the meanings given in general formula I and Hal is halogen isreacted with a nucleophile of general formula V

    θSR.sup.17                                           (V)

in which R¹⁷ has the meaning given in general formula I, or when R⁵ isnitro and R⁶ is --S(O)_(n) R¹⁷, in which n is 1 or 2,

G) a compound of general formula Ih ##STR22## in which R¹, R², R³, R⁴and R¹⁷ have the meanings given in general formula I, is subjected to astepwise oxidation with m-chloroperbenzoic acid, or when R⁵ is cyano

H) a compound of general formula IIa ##STR23## in which R¹ and R² havethe meanings given in general formula I, is reacted with a compound ofgeneral formula IIIc ##STR24## in which Y is C₁ -C₆ -alkoxy, hydroxy orhalogen, or when R⁵ is nitro,

I) a compound of general formula Ii ##STR25## in which R¹ and R² havethe meanings given in general formula I, is nitrated in known manner, or

J) a compound of general formula Ij ##STR26## in which R¹, R² and R⁵have the meanings given in general formula I, is brominated in knownmanner, or when when R⁵ is halogen,

K) a compound of general formula II ##STR27## in which R₁, R² and R³have the meanings given in general formula I, is reacted with a compoundof general formula IIIc ##STR28## in which Y' is C₁ -C₆ -alkoxy,dimethylamino or halogen, to first give compound of formula Il ##STR29##in which R¹, R² and R³ have the meanings given in general formula I, andthis compound is then diazotised in known manner with sodium nitrite andconverted to the corresponding halide, or

L) a compound of general formula Ik ##STR30## in which R¹, R² and R⁶have the meanings given in general formula I, is treated with ahalogenating agent, or

M) a compound of general formula Im ##STR31## in which R¹, R² and R³have the meanings given in general formula I, and R⁶ is C₁ -C₄ -alkyl,(optionally substituted by one or more halogens) or is a C₂ -C₈ -alkyl,interrupted by one or more oxygens, is converted in known manner to thenitrile of general formula I, or when R⁶ is --NR¹¹ R¹²,

N) a compound of general formula In ##STR32## in which R¹, R² and R³have the meanings given in general formula I, is reacted with an aminein a solvent, or when R⁶ is --NR¹¹ R¹², in which R¹¹ is hydrogen and R¹²is C₁ -C₆ -alkyl,

O) a compound of general formula Il ##STR33## in which R¹, R² and R³have the meanings given in general formula I, is reacted with a trialkylortho ester and then reduced, or

P) a compound of general formula Io ##STR34## in which R¹, R² and R³have the meanings given in general formula I, and R¹² is C₁ -C₆ -alkylis reacted with an base and an alkylating agent or an acid chloride, orwhen R⁶ is --NR¹¹ R¹², in which R¹¹ and R¹² are C₁ -C₆ -alkyl,

Q) a compound of general formula Il ##STR35## in which R¹, R² and R³have the meanings given in general formula I, is reacted withapproximately 2 mole of base and 2 mole of a suitable alkylating agent,or

R) a compound of general formula Il ##STR36## in which R¹, R² and R³have the meanings given in general formula I, is reacted with or withouta base and a suitable acid chloride, or

S) a compound of general formula Ip ##STR37## in which R¹, R², R³ andR²¹ have the meanings given in general formula I, is reacted with a baseand a suitable alkylating agent, or

T) a compound of general formula In ##STR38## in which R¹, R² and R³have the meanings given in general formula I and R⁵ is cyano or nitro,is reacted with an oxygen, nitrogen, sulfur or carbon nucleophile, orwhen R⁶ is substituted methyl

U) a compound of general formula Iq ##STR39## in which R¹, R², R³, R⁴and R⁵ have the meanings given in general formula I, is reacted with aLewis acid, or

V) a compound of general formula Ir ##STR40## in which R¹, R², R³, R⁴and R⁵ have the meanings given in general formula I, is treated with ahalogenating agent, or

W) a compound of general formula Is ##STR41## in which R¹, R², R³, R⁴and R⁵ have the meanings given in general formula I, is reacted with anoxygen, nitrogen, sulfur or carbon nucleophile, or when R₆ is mercapto

X) a compound of general formula It ##STR42## in which R¹, R², R³ and R⁴have the meanings given in general formula I, is treated with sodiumhydrogen sulfide, or

Y) a compound of general formula Iu ##STR43## in which R¹, R², R³ and R⁴have the meanings given in general formula I, is treated with a suitablealkylating agent, or

Z) a compound of general formula Iv ##STR44## in which R₁, R², R³ and R⁴have the meanings given in general formula I, and R^(x) is C₁ -C₄-alkyl, is oxidised in stages.

The compounds of the invention of general formula I, in which R⁵ isnitro and R⁶ is halogen, can also be prepared according to the processdescribed in DE 3501323.

The compounds of the invention of general formula I, in which R⁵ is thegroup --C(O)R¹⁰ and R⁶ is amino, can also be prepared according to theprocess described in Collect. Czech. Chem. Commun. 55, 1038-48 (1990).

The compounds of the invention of general formula I, in which R⁶ is thegroup -NR¹¹ R ¹², can also be prepared according to the known processesdescribed in DE 3 707 686, DE 3 543 034, EP 224 831, DE 3 543 035, JP57167972 and DE 2 747 531.

The compounds of the invention of general formula I, in which R¹⁴ is thegroup -OR¹⁸ or -NR¹⁹ R²⁰, can be prepared from compounds of generalformula I, in which R⁶ is amino according to the known processesdescribed in Chem. Soc. Rev. 4, 231-50 (1975) and J. March, AdvancedOrganic Chemistry, 1985, p. 370.

The compounds of the invention of general formula I, in which R⁵ iscyano or nitro and R⁶ is C₁ -C₄ -alkyl, can be prepared according toknown processes (J. Heterocyclic Chem. 24, 1669 (1987), ibid. 24, 739(1987).

The reactions are suitably carried out by reacting the compounds offormulae II, IIa or III in a suitable solvent at a temperature between-30° and 150° C., preferably at room temperature.

As halogenating agent there can be used for example sulfuryl chloride,sodium hypochlorite, N-chlorosuccinimide, N-bromosuccinimide, bromine orchlorine.

Leaving groups in process variant E are chloro or bromo.

The nitration in process variant I) is suitably carried out in knownmanner with nitric acid in acetic anhydride. The reaction temperaturelies in the region of -10° to 140° C.

The process variant J) is suitably carried out in a solvent at atemperature of -20° C. up to the boiling point of the solvent.

As brominating agent in process variant J) there can be used, forexample N-bromosuccinimide or bromine.

The reaction of compounds of general formula Il is suitably carried bythe method described in J. March, Advanced Organic Chemistry, 1985, p.647.

The process variant L) is generally carried out in a suitable solvent,preferably acetonitrile or dichloromethane, at a temperature of between-10° C. and 80° C.

Process variant M) is generally carried out according to the methoddescribed in Tetrahedron Letters, 1977 p. 1813.

Process variant O) is generally carried out according to the knownmethods (J. March, Advanced organic Chemistry, 1985, p. 798-800 andliterature cited there).

Suitable bases for process variants P), Q), R) and S) include forexample alkali metal and alkaline earth metal hydroxides, sodiummethanolate, alkali metal hydrides, alkali metal and alkaline earthmetal carbonates, tertiary aliphatic and aromatic amines, such astriethylamine and pyridine as well as heterocyclic bases.

Process variant T) is generally carried out for example according tomethods described in J. Heterocyclic Chem. 25, 555 (1988).

The preparation can be carried out with or without a solvent. Shouldneed arise, such solvent or diluents can be used which are inert to thereactants. Examples of such solvents or diluents are aliphatic,alicyclic and aromatic hydrocarbons, each of which can be optionallychlorinated, such as for example hexane, cyclohexane, petroleum ether,naphtha, benzene, toluene, xylene, methylene chloride, chloroform,carbon tetrachloride, ethylene dichloride, trichloroethane andchlorobenzene, ethers, such as for example diethyl ether, methyl ethylether, methyl t-butyl ether, diisopropyl ether, dibutyl ether, dioxaneand tetrahydrofuran, ketones, such as for example acetone, methyl ethylketone, methyl isopropyl ketone and-methyl isobutyl ketone, nitriles,such as for example acetonitrile and propionitrile, alcohols, such asfor example methanol, ethanol, isopropanol, butanol, tert-butanol,tert-amyl alcohol and ethylene glycol, esters, such as for example ethylacetate and amyl acetate, amides, such as for example dimethylformamideand dimethylacetamide, sulfoxides, such as for example dimethylsulfoxide and sulfones such as for example sulfolane, bases, such as forexample pyridine and triethylamine, carboxylic acids such as for exampleacetic acid, and mineral acids such as for example sulfuric acid andhydrochloric acid.

The compounds of the invention can be worked up in conventional manner.Purification can be achieved by crystallisation or columnchromatography.

The compounds of the invention are, as a rule, colourless or slightlyyellow crystalline or liquids or substances that are highly soluble inhalogenated hydrocarbons, such as methylene chloride or chloroform,ethers, such as diethyl ether or tetrahydrofuran, alcohols, such asmethanol or ethanol, ketones, such as acetone or butanone, amides, suchas dimethylformamide, and also sulfoxides, such as dimethyl sulfoxide.

The intermediate compounds of general formula II ##STR45## in which R¹,R² and R³ have the meanings given in general formula I can be preparedin known manner (e.g. JP 62158260) from compounds of general formula VI##STR46## in which R¹, R² and R³ have the meanings given in generalformula I.

The compounds of general formula II in which R¹ and R² together form thegroup --(CH₂)_(v) -- and R³ is hydrogen, can be prepared by treating acompound of general formula IIIc ##STR47## with hydrazine with additionof a base. The compound of general formula IlIc can be prepared byreacting a compound of general formula IIId ##STR48## and a1,1-dihaloethylene.

The compounds of general formula VI, in which R¹ and R² have themeanings given in general formula I and R³ is halogen, can be preparedby reacting a compound of general formula VI in which R³ is hydrogen,with a halogenating agent.

The compounds used as starting materials for compounds of generalformula VI, are of general formula VII ##STR49## in which R¹ has themeaning given in general formula I, and can be prepared for example, bya process in which, in the case when R² is C₁ -C₄ -alkyl, optionallysubstituted by halogen,

a) a compound of general formula VIII, VIIIa or IX ##STR50## in which R²is C₁ -C₄ -alkyl, optionally substituted by halogen, is reacted with acompound of general formula X

    R.sup.1 --NHNH2                                            (X)

in which R¹ has the meaning given in general formula I, optionally inthe presence of a solvent, or when R² is C₁ -C₄ -alkylthio, optionallysubstituted by one or more halogens,

b) a compound of general formula XI ##STR51## in which R³⁵ is cyano orthe group --COOR³⁶, in which R³⁶ is C₁ -C₄ -alkyl, is reacted with acompound of general formula X, optionally in the presence of a solvent,e.g. water, to give first a compound of general formula XII ##STR52## inwhich R¹ has the meaning given in general formula I and R³⁵ has themeaning given above, which is then reacted with a compound of generalformula XIII

    R.sup.37 Q (XIII)

in which R³⁷ is C₁ -C₄ -alkyl, optionally substituted by one or morehalogens, and Q is a leaving group, and the resulting compound ofgeneral formula XIV ##STR53## is saponified and decarboxylated accordingto known literature methods (e.g. Zeitschrift fur Chemie 420, (1968)),or

c) a compound of general formula XV ##STR54## in which R³⁵ is cyano orthe group --COOR³⁶, in which R³⁶ is C₁ -C₄ -alkyl, and R³⁷ is C₁ -C₄-alkyl, optionally substituted by one or more halogens, is reacted witha compound of general formula X, optionally in the presence of asolvent, e.g. water, to give a compound of general formula XIV, or whenR² is C₁ -C₄ -alkoxy, optionally substituted by one or more halogens

d) a compound of general formula XVI ##STR55## in which R¹ has themeaning given in general formula I, is reacted with a compound ofgeneral formula XIII, in the presence of a base, or

h) a compound of general formula XVII ##STR56## in which R¹ has themeaning given in general formula I and Z is C₁ -C₄ -alkyl, is reacted,in the presence of a base, with a compound of general formula XIII

    R.sup.37 Q                                                 (XIII)

in which R³⁷ is C₁ -C₄ -alkyl, optionally substituted by one or morehalogens, and Q is a leaving group, and the resulting compound ofgeneral formula XVIII ##STR57## in which R¹ has the meaning given ingeneral formula I, R³⁷ is C₁ -C₄ -alkyl, optionally substituted by oneor more halogens, and Z is C₁ -C₄ -alkyl, is reacted with ammonia andthe resulting compound of general formula XIX ##STR58## in which R¹ hasthe meaning given in general formula I and R³⁷ is C₁ -C₄ -alkyl,optionally substituted by one or more halogens, is reacted with sodiumhydroxide and a halogen, or when R³ in general formula I is halogen,

f) a compound of general formula XVIII or XIX ##STR59## in which R¹ hasthe meaning given in general formula I, R³⁷ is C₁ -C₄ -alkyl, optionallysubstituted by one or more halogens, and Z is C₁ -C₄ -alkyl, is reactedwith a halogenating agent to give a compound of general formula XVIIIaand XIXb ##STR60## in which R¹, R³⁷ and Z have the meanings given ingeneral formula XVIII and XIX, or

g) a compound of general formula XIXa ##STR61## in which R¹ has themeaning given in general formula I, R³⁷ is C₁ -C₄ -alkyl, optionallysubstituted by one or more halogens, and Hal is halogen, is reacted withsodium hydroxide and bromine to give a compound of general formula XX##STR62## in which R¹ R³⁷ and Hal have the meanings given in formulaXIXa, or when R¹ and R² together form a tri- or tetramethylene group

h) a compound of general formula XXI ##STR63## in which n is 2 or 3, isreacted with hydrazine and the resulting 3(5)-amino-5(3)-hydroxyalkylpyrazole of general formula XXII ##STR64## in which n is 2or 3, is reacted with hexane-2,5-dione, phthalic anhydride ortetrahydrophthalic anhydride, in a similar manner to known literaturemethods (Bull. Chem. Soc. Jp., 44, 2856-8 (1971), or EP 305826), to givea compound of general formula XXIII ##STR65## in which n is 2 or 3 and Qis an amino protecting group, such as e.g. Q₁, Q₂ or Q₃ ##STR66## andthis is cyclised using the Mitsunobu variant (Synthesis, 1 (1981)), togive a compound of general formula XXIV ##STR67## in which n is 2 or 3,and then in the case when Q is Q₁, this is treated with hydroxylamine asdescribed in J. Org. Chem., 49, 1224-1227 (1984), and in the case when Qis Q₂ or Q₃, this is treated with hydrazine, in a similar manner toknown literature methods (Org. Synthesis, Coll. Vol., 3, 148 (1955)).

The starting materials of general formula XXI can be prepared in knownmanner (Chem. Ber., 109(1), 253-60, 1976).

The compounds of general formula Ii, used as starting materials, can beprepared by decarboxylating a compound of general formula XXV ##STR68##in which R¹ and R² have the meanings given in general formula I.

The compounds of general formula XXV can be prepared by saponifying acompound of general formula XXVI ##STR69## in which R¹ and R², have themeanings given under general formula I and R⁷ is C₁ -C₄ -alkyl.

The compounds of general formula XXVI can be prepared by reacting acompound of general IIa, in which R¹ and R² have the meanings givenunder general formula I with a compound of general formula XXVII##STR70## in which R⁷ is C₁ -C₄ -alkyl and Y is C₁ -C₆ -alkoxy, hydroxyor halogen.

The intermediates of general formula Ij, can be prepared in an analogousway to process described above in which instead of the compounds ofgeneral formulae lIa and Ii the corresponding compounds of generalformula XXVIII and/or XXIX ##STR71## are used.

The intermediates of general formula Ik, can be prepared by reacting acompound of general formula IIb ##STR72## in which R¹ and R² have themeanings given in general formula IIb in an analogous way to processesdescribed above.

The intermediates of general formula Im, in which R⁶ is C₁ -C₄ -alkyl,optionally substituted by one or more halogens or C₂ -C₈ -alkyl,interrupted by one or more oxygen atoms, can be prepared converting acompound of general formula Iq ##STR73## in which R¹, R² and R³ have themeanings given in general formula I, R⁶ is C₁ -C₄ -alkyl, optionallysubstituted by one or more halogens or C₂ -C₈ -alkyl, interrupted by oneor more oxygen atoms, and R⁷ is C₁ -C₄ -alkyl, in known manner to theamide.

The compounds of general formula Iq can be prepared in known manner (J.Heterocyclic Chem 24, 1669 (1987), ibid. 24, 739 (1987)).

The preparation of the intermediates can be carried out with or withouta solvent. Should need arise, a solvent mentioned above can be used.

The named starting materials are either known in the or can be preparedin similar manner to known methods.

The compounds of the invention show a good herbicidal activity againstbroad leaved weeds and grasses. A selective use of the compounds of theinvention in various crops is possible for example in rape, beet, soyabeans, cotton, rice, barley, wheat and other cereals. Individual activesubstances are particularly suitable as selective herbicides in beet,cotton, soya, maize and cereals. However the compounds can be used forcontrol of weeds in permanent crops, such as for example forestry,ornamental trees, fruit, vine, citrus, nut, banana, coffee, tea, rubber,oil palm, cocoa, berry fruit and hop plantations.

The compounds of the invention can used for example against thefollowing plant species:

Dicotyledonous weeds of the species: Sinapis, Lepidium, Galium,Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Brassica,Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea,Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum,Rorippa, Lamium, Veronica, Abutilon, Datura, Viola, Galeopsis, Papaver,Centaurea and Chrysanthemum.

Monocotyledonous weeds of the species: Avena, Alopecurus, Echinochloa,Setaria, Panicum, Digitaria, Poa, Eleusine, Brachiaria, Lolium, Bromus,Cyperus, Agropyron, Sagittaria, Monocharia, Fimbristylis, Eleocharis,Ischaemum and Apera.

The rates of use vary depending on the manner of pre- and postemergentuse between 0.001 and 5 kg/ha.

The compounds of the invention can also be used as defoliants,desiccants and total herbicides.

The compounds of the invention can be used either alone or in admixturewith one another or with other active agents. Optionally, otherplant-protective agents or pesticides can be added, depending on thepurpose for the treatment. When it is desired to broaden the spectrum ofactivity, other herbicides can also be added. Herbicidally active mixingpartners suitable in this connection include for example, the activeagents listed in Weed Abstracts, vol. 40, No. 1, 1991, under the heading"Lists of common names and abbreviations employed for currently usedherbicides and plant growth regulators in Weed Abstracts".

An improvement in the intensity and speed of action can be obtained, forexample, by addition of suitable adjuvants, such as organic solvents,wetting agents and oils. Such additives may allow a decrease in thedose.

The designated active ingredients or their mixtures can suitably beused, for example, as powders, dusts, granules, solutions, emulsions orsuspensions, with the addition of liquid and/or solid carriers and/ordiluents and, optionally, binding, wetting, emulsifying and/ordispersing adjuvants.

Suitable liquid carriers are, for example aliphatic and aromatichydrocarbons, such as benzene, toluene, xylene, cyclohexanone,isophorone, dimethyl sulfoxide, dimethylformamide and other mineral-oilfractions and plant oils.

Suitable solid carriers include mineral earths, e.g. bentonite, silicagel, talcum, kaolin, attapulgite, limestone, silicic acid and plantproducts, e.g. flours.

As surface-active agents there can be used for example calciumlignosulfonate, polyoxyethylenealkylphenyl ethers, naphthalenesulfonicacids and their salts, phenolsulfonic acids and their salts,formaldehyde condensates, fatty alcohol sulfates, as well as substitutedbenzenesulfonic acids and their salts.

The percentage of the active ingredient(s) in the various preparationscan vary within wide limits. For example, the compositions can containabout 10 to 90 percent by weight active ingredients, and about 90 to 10percent by weight liquid or solid carriers, as well as, optionally up to20 percent by weight of surfactant.

The agents can be applied in customary fashion, for example with wateras the carrier in spray mixture volumes of approximately 100 to 1,000l/ha. The agents can be applied using low-volume or ultra-low-volumetechniques or in the form of so-called microgranules.

The preparation of these formulations can be carried out in knownmanner, for example by milling or mixing processes. Optionally,individual components can be mixed just before use for example by theso-called commonly used tank-mixing method.

Formulations can be prepared, for example, from the followingingredients.

A) Wettable Powder

20 percent by weight active ingredient

35 percent by weight fuller's earth

8 percent by weight calcium lignosulfonate

2 percent by weight sodium salt of N-methyl-N-oleyltaurine

25 percent by weight silicic acid

B) Paste

45 percent by weight active ingredient

5 percent by weight sodium aluminium silicate

15 percent by weight cetyl polyglycol ether with 8 mole ethylene oxide

2 percent by weight spindle oil

10 percent by weight polyethylene glycol

23 percent by weight water

C) Emulsifiable Concentrate

20 percent by weight active ingredient

75 percent by weight isophorone

5 percent by weight of a mixture of the sodium salt ofN-methyl-N-oleyltaurine and calcium lignosulfonate

The following examples illustrate the preparation of compounds accordingto the invention.

EXAMPLE 1.0

4-Acetyl-5-amino-1-(3-chloro-4,5,6,7-tetrahydropyrazolo-1,5-a!pyridin-2-yl)pyrazole

0.56 g (3 mmol) 3-Chloro-2-hydrazino-4,5,6,7-tetrahydro-pyrazolo1,5-a!pyridine was dissolved in 5 ml ethanol and treated with 0.42 g (3mmol) 2-ethoxymethylen-3-oxobutyro-nitrile. After heating under refluxfor 3 hours, the mixture was concentrated and the residue purified bysilica gel chromatography (hexane/ethyl acetate 1:1).

Yield: 0.75 g=89.4% of theory

mp: 153°-154° C.

EXAMPLE 1.1

5-Amino-1-(3-chloro-4,5,6,7-tetrahydropyrazolo-1,5-a!pyridin-2-yl)-4-thioacetylpyrazole

0.28 g (1 mmol) 4-Acetyl-5-amino-1-(3-chloro-4,5,6,7-tetrahydropyrazolo1,5-a!pyridin-2-yl)pyrazole was dissolved in 5 ml dimethoxyethane andtreated with 0.28 (0.6 mmol) Lawesson's reagent. After heating underreflux for 2 hours with stirring, the reaction solution was poured intowater and extracted with ethyl acetate. The organic phase was washedwith saturated aqueous sodium chloride, dried over magnesium sulfate andconcentrated. The residue was purified by silica gel columnchromatography. (Hexane/ethyl acetate 1:1).

Yield: 0.21 g=71% of theory

mp: 166°-167° C.

EXAMPLE 1.2

N- 1-(3-Chloro-4,5,6,7-tetrahydropyrazolo1,5-a!pyridin-2-yl)-4-nitro-5-pyrazolyl!propionamide

8.72 g (29.7 mmol) N- 1-(3-Chloro-4,5,6,7-tetrahydro-pyrazolo1,5-a!pyridin-2-yl)-5-pyrazolyl!propionamide was suspended in 33 mlacetic acid. Under ice cooling, at 0°-5° C., 3.31 g (32.5 mmol) aceticanhydride was added. 1.93 g (31 mmol) Fuming nitric acid was addeddropwise. After stirring for 6 hours at room temperature, the mixturewas concentrated. The residue was taken up in dichloromethane,neutralised with aqueous sodium hydrogen carbonate and washed withaqueous sodium chloride. The organic phase was dried over magnesiumsulfate and concentrated. The residue was purified by silica gelchromatography (hexane/ethyl acetate 1:1).

Yield: 6.03 g=60% of theory

mp: 46°-49° C.

EXAMPLE 2.0

N-1-(4-Chloro-5-difluoromethoxy-1-methyl-3-pyrazolyl)-4-nitro-5-pyrazoylyl!-2,2,2-trifluoroacetamide

0.79 g (2.1 mmol) N-1-(5-Difluoromethoxy-1-methyl-3-pyrazolyl)-4-nitro-5-pyrazolyl!-2-2,2-trifluoroacetamidewas suspended in 35 ml dichloromethane and treated with 0.17 ml sulfurylchloride. The mixture was stirred for one hour at room temperature andconcentrated.

Yield: 0.77 g=89.5% of theory

mp: 136°-139° C.

EXAMPLE 2.1

N-1-(4-Chloro-5-difluoromethoxy-1-methyl-3-pyrazolyl)-4-nitro-5-pyrazolyl!acetamide

1.3 g (5.0 mmol)5-Amino-1-(4-chloro-5-difluoromethoxy-1-methyl-3-pyrazolyl)pyrazole wasdissolved in 20 ml acetic acid and treated with 0.55 g (5.4 mmol) aceticanhydride. After stirring for 2 hours at room temperature the reactionsolution was cooled to 0° C. and 0.4 g (6.4 mmol) concentrated nitricacid added. After stirring for 8 hours at room temperature, the reactionmixture was poured into ice water and extracted with ethyl acetate. Theorganic phase was dried over magnesium sulfate and concentrated. Theresidue was purified by silica gel column chromatography (hexane/ethylacetate 1:1).

Yield: 1.4 g=81.5% of theory

mp: 132° C.

EXAMPLE 3.1

5-Amino-4-nitro-1-(4-bromo-5-difluoromethoxy-1-methyl-3-pyrazolyl)pyrazole

8.3 g (0.052 mol) Bromine was added dropwise at room temperature to 13 g(0.047 mol)5-amino-4-nitro-1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)pyrazoledissolved in 260 ml acetic acid and the mixture stirred for 30 minutes.It was then concentrated and the residue taken up in the ethyl acetateand shaken with 5% aqueous sodium hydrogen carbonate. The phases wereseparated and the organic phase dried over magnesium sulfate. This wasconcentrated and the residue purified by silica gel columnchromatography (hexane/ethyl acetate 3:1).

Yield: 8.3 g=49.6% of theory

mp: 148° C.

Preparation of the starting materials

1. 5-Amino-4-nitro-1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)-pyrazole

15 g (0.065 mol)5-Amino-1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)pyrazole was dissolvedin 60 ml acetic acid and treated with 7.35 g (0.072 mol) aceticanhydride. After stirring at room temperature for 3 hours, the reactionmixture was cooled to 10° C. 4.95 g (0.078 mol) Fuming nitric acid wasadded dropwise and the mixture treated with 8.0 g (0.078 mol) aceticanhydride. After stirring for 18 hours at room temperature, the reactionmixture was added to 500 ml ice-water. It was extracted three times withethyl acetate, the organic phases were washed with water andconcentrated. The residue was treated with 80 ml ethanol and 40 mlconcentrated hydrochloric acid. After heating for 8 hours under reflux,the ethanol was removed and the residue extracted with ethyl acetate.The concentrated ethyl acetate phases were washed with saturated aqueoussodium hydrogen carbonate, dried over magnesium sulfate andconcentrated. The residue was recrystallised from diisopropyl ether andethyl acetate.

Yield: 10 g=56% of theory

mp: 140° C.

2. 5-Amino-1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)-pyrazole

16.5 (0.06 mol)5-Amino-1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)-4-pyrazolecarboxylicacid was heated at 210° C. for 5 minutes and then cooled. The congealedmelt was recrystallised from diisopropyl ether.

Yield: 12.6 g=92% of theory

mp: 106°-107° C.

3.5-Amino-1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)-4-pyrazolecarboxylicacid

18.9 g (0.06 mol) Ethyl5-Amino-1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)-4-pyrazolyl-4-pyrazolecarboxylatewas dissolved in 150 ml 50% ethanol and treated with 15 ml 45% causticsoda. The mixture was heated for 2 hours at 80° C., the ethanoldistilled, the residue treated with ice-water and acidified withconcentrated hydrochloric acid. The residue was removed by suctionfiltration, washed with water and dried in vacuo at 75° C.

Yield: 16.7 g=97% of theory

mp: 173° C. (dec.)

4. Ethyl5-Amino-1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)-4-pyrazolyl-4-pyrazolecarboxylate

19 g (0.1 mol) 5-Difluoromethoxy-3-hydrazino-1-methyl-pyrazole wasdissolved in 100 ml ethanol. 18.05 g (0.1 mol) Ethylethoxymethylenecyanoacetate was added and the mixture heated for 1.5hours at boiling. After cooling, the precipitated product was removed bysuction filtration, washed with some ethanol and dried.

Yield: 18.95 g=59% of theory

mp: 168°-169° C.

5. 5-Difluoromethoxy-3-hydrazino-1-methylpyrazole

39.8 g (0.25 mol) 3-Amino-5-difluoromethoxy-1-methyl-pyrazole wasdissolved in 224 ml water and 450 ml concentrated hydrochloric acid. At-10° C., 18.55 g (0.27 mol) sodium nitrite in 80 ml water was addeddropwise. After stirring for 1 hour at -10° C., 137.6 g tin(II)chloride,dissolved in 180 ml concentrated hydrochloric acid, was added, dropwise,at this temperature. After a further hour stirring at -10° C., 805 ml32% caustic soda was added dropwise at this temperature. The reactionmixture was shaken 8 times with ethyl acetate, the combined organicphases washed with saturated aqueous sodium chloride, dried overmagnesium sulfate and concentrated.

Yield: 42.24 g=97.2% of theory

EXAMPLE 3.2

5-Amino-1-(4-bromo-5-difluoromethoxy-1-methyl-3-pyrazolyl)-4-pyrazolecarbonitrile

5.0 g (20 mmol)5-Amino-1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)-4-pyrazolecarbonitrilewas dissolved in 80 ml acetic acid. At room temperature, 1.2 ml (23mmol) bromine was added, dropwise. After stirring for 15 minutes, themixture was concentrated and stirred with diisopropyl ether/propanol.The solid material was suction filtered and dried.

Yield: 5.7 g=87% of theory

mp: 160° C.

EXAMPLE 3.3

5-Amino-1-(3-bromo-4,5,6,7-tetrahydropyrazolo-1,5-a!-pyridin-2-yl)-4-nitropyrazole

3.6 g (12.7 mmol) 5-Amino-1-(3-bromo-4,5,6,7-tetrahydro-pyrazolo1,5-a!pyridin-2-yl)pyrazole was suspended in 15 ml acetic acid andtreated with 1.23 ml (13.0 mmol) acetic anhydride. The mixture wasstirred for 5 hours at room temperature. 1.5 ml (15.9 mmol) aceticanhydride was added and then, with ice-bath cooling, 0.66 ml (15.5 mmol)fuming nitric acid was added, dropwise. After stirring for 12 hours atroom temperature, the mixture was concentrated. The residue wasdissolved in 30 ml ethanol and treated with 11.2 ml concentratedhydrochloric acid. After heating for 3 hours under reflux, the mixturewas concentrated and the residue taken up in water and ethyl acetate. Itwas made basic with 2N aqueous sodium hydroxide and the organic phaseseparated. The aqueous phase was extracted twice with ethyl acetate. Thecombined organic phases were washed once with water and once withsaturated aqueous sodium chloride. The organic phase was dried andconcentrated. The residue was recrystallised from ethyl acetate.

EXAMPLE 4.1

1-(3-Chloro-4,5,6,7-tetrahydropyrazolo1,5-a!pyridin-2-yl)-5-diethylamino-4-pyrazolecarbonitrile

10.45 g (0.35 mol) Sodium hydride (80%) was added to 100 mltetrahydrofuran and cooled to 0° C. In a nitrogen atmosphere, asuspension of 43.6 g (0.17 mol)5-amino-1-(3-chloro-4,5,6,7-tetrahydropyrazolo-1,5-a!pyridin-2-yl)-4-pyrazolecarbonitrile in 500 ml tetrahydrofuran wasadded dropwise. The mixture was stirred for 1.5 hours. Then 31.4 ml(0.38 mol) iodoethane in 20 ml tetrahydrofuran was added dropwise at 15°C. After stirring for three hours at 15° C., the mixture was cooled.Water was then added dropwise and the mixture extracted with ethylacetate. The organic phase was separated, dried and concentrated. Theresidue was recrystallised from ethyl acetate.

Yield: 47.3 g=89.4% of theory

mp: 68°-70° C.

EXAMPLE 4.2

1-(3-Chloro-4,5,6,7-tetrahydropyrazolo1,5-a!-pyridin-2-yl)-5-(ethylmethylamino)-4-pyrazolecarbonitrile

23.3 g (88.7 mmol) 5-Amino-1-(3-chloro-4,5,6,7-tetrahydro-pyrazolo1,5-a!pyridin-2-yl)-4-pyrazolecarbonitrile, 202 ml (1,21 mmol) triethylorthoformate and 10 drops trifluoroacetic acid was heated for 5 hourswith removal of water in a water bath at a temperature of 150° C. Thereaction solution was concentrated, the residue was suspended in 250 mlethanol and treated, portionwise, with cooling with 4.2 g (106.4 mmol)sodium borohydride. The mixture was heated to reflux until no more gasevolution was observed. Then the mixture was concentrated and theresidue carefully added to ice-water. The mixture was extracted 3 timeswith methylene chloride and the extracts dried. The organic phase wasconcentrated. 2.61 g (87.1 mmol) Sodium hydride (80%) was added to 150ml tetrahydrofuran and at 0° C., 24.1 g (87.1 mmol) of the resulting1-(3-chloro-4,5,6,7-tetrahydropyrazolo-1,5-a!pyridin-2-yl)-5-methylamino-4-pyrazolecarbonitrile in 500 mltetrahydrofuran was added dropwise. After stirring for 1 hour at roomtemperature, 7.82 ml (95.8 mmol) iodoethane was added and the mixtureheated at 70° C. for 3 hours. Water was added dropwise and the mixtureextracted 3 times with ethyl acetate. The organic phase was separated,dried and concentrated. The residue was recrystallised from ethylacetate.

Yield: 18.97 g=71% of theory

mp: 68°-69° C.

EXAMPLE 4.3

5-Bromo-1-(4-chloro-5-difluoromethoxy-1-methyl-3-pyrazolyl)-4-Pyrazolecarbonitrile

5 5.68 g (19.7 mmol)5-Amino-1-(4-chloro-5-difluoromethoxy-1-methyl-3-pyrazolyl)-4-pyrazolecarbonitrilewas dissolved in 66.3 ml hydrobromic acid (47%) and the mixture cooledto -6° C. Under a nitrogen atmosphere, 2.36 g (34.2 mmol) sodium nitritein 5.9 ml water was added dropwise. The mixture was stirred for 15minutes at this temperature and heated to room temperature. 200 ml waterwas then added and the mixture extracted 4 times with methylenechloride. The organic phase was washed with saturated aqueous sodiumhydrogen carbonate, dried over magnesium sulfate and concentrated.

Yield: 6.94 g=99.5% of theory

mp: 78° C.

Preparation of the starting materials

1.5-Amino-1-(4-chloro-5-difluoromethoxy-1-methyl-3-pyrazolyl)-4-pyrazolecarbonitrile

5.0 g (19.7 mmol)5-Amino-1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)-4-pyrazolecarbonitrilewas dissolved in 180 ml acetonitrile and 2.65 g (19.7 mmol) sulfurylchloride added dropwise. The mixture was stirred for one hour at roomtemperature and concentrated.

30 Yield: 5.68 g=99.5% of theory

mp: 140°-142° C.

2.5-Amino-1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)-4-pyrazolecarbonitrile

22.5 g (0.13 mol) 5-Difluoromethoxy-3-hydrazino-1-methyl-pyrazole wasdissolved in 310 ml ethanol and treated with 15.4 g (0.13 mol)ethoxymethylenemalononitrile. After the mixture had been heated underreflux for one hour it was cooled. The precipitate was suction filteredand washed with a small amount of ethanol.

Yield: 19.28 g=60% of theory

mp: 141°-143° C.

3. 5-Difluoromethoxy-3-hydrazino-1-methylpyrazole

39.8 g (0.25 mol) 3-Amino-5-difluoromethoxy-1-methyl-pyrazole wasdissolved in 225 ml water and 450 ml concentrated hydrochloric acid. At-10° C., 18.55 g (0.27 mol) sodium nitrite in 80 ml water was addeddropwise. After stirring for one hour at -10° C., 137.6 gtin(II)chloride, dissolved in 180 ml concentrated hydrochloric acid, wasadded dropwise at this temperature. After stirring for a further hour at-10° C., 805 ml 32% caustic soda was added dropwise at this temperatureto the reaction mixture. The mixture was shaken 8 times with ethylacetate, the combined organic phases washed with aqueous saturatedsodium chloride, dried over magnesium sulfate and concentrated.

Yield: 42.24 g=97.2% of theory

4. 3-Amino-5-difluoromethoxy-1-methylpyrazole

71.7 g (1.79 mol) Sodium hydroxide was added to 600 ml water and themixture cooled to -5° C. At this temperature, 57.3 g (0.36 mol) brominewas added dropwise at such a rate that the temperature did not riseabove 0° C. Then 57.1 g (0.3 mol)3-carbamoyl-5-difluoromethoxy-1-methyl-pyrazole was added portionwise at0° C. The reaction mixture was stirred for one hour at 80° C. and thensaturated with sodium chloride. The precipitate which formed was suctionfiltered off. The filtrate was shaken 6 times with the ethyl acetate.The organic phase was dried over magnesium sulfate and concentrated. Theprecipitate which had been removed was dissolved in 500 ml water and thesolution heated to boiling point for one hour. The reaction solution wassaturated with sodium chloride and shaken 6 times with ethyl acetate.The organic phase was dried with magnesium sulfate and concentrated.

Yield: 34.2 g=70.5% of theory

mp: 57° C.

5. 3-Carbamoyl-5-difluoromethoxy-1-methylpyrazole

80.6 g (0.39 mol) 3-Methoxycarbonyl-5-difluoromethoxy-1-methylpyrazoleand 300 ml aqueous ammonia (33%) was stirred for one hour under reflux.The reaction solution was cooled, the precipitate suction filtered offand washed with water and diisopropyl ether.

Yield: 58.9 g=78.8% of theory

mp: 154° C.

6. 5-Difluoromethoxy-3-methoxycarbonyl-1-methylpyrazole

67.6 g (0.43 mol) 5-Hydroxy-3-methoxycarbonyl-1-methyl-pyrazole and299.2 g (2.17 mol) potassium carbonate was dissolved in 1500 mldimethylformamide and heated to 70° C. At this temperaturechlorodifluoromethane was introduced over 2 hours and the mixturestirred at 80° C. for 1.5 hours. The reaction mixture was added to waterand extracted 6 times with ethyl acetate. The combined organic phaseswere washed with saturated aqueous sodium chloride and dried overmagnesium sulfate. The reaction solution was concentrated.

Yield: 80.6 g=90.3% of theory

7. 5-Hydroxy-3-methoxycarbonyl-1-methylpyrazole

102.3 g (0.72 mol) Dimethyl acetylenedicarboxylate was added to 1000 mlether and the mixture cooled to -5° C. in an ice-methanol bath. 33 g(0.72 mol) methylhydrazine in 100 ml ether was added dropwise at a ratethat the inner temperature did not rise above 0° C. The mixture wasstirred for one hour at 0° C., the precipitate suction filtered off,washed with ether and dried at 40° C. in vacuo. The intermediate wasimmersed in an oil-bath heated to 120° C. The reaction product wasrecrystallised from methanol.

Yield: 67.6 g=60.1% of theory

mp: 197° C.

8. 4-Chloro-5-difluoromethoxy-3-methoxycarbonyl-1-methyl-pyrazole

2.1 g (10 mmol) 5-Difluoromethoxy-3-methoxycarbonyl-1-methylpyrazole,dissolved in 30 ml methylene chloride, was treated with 1.35 g (10 mmol)sulfuryl chloride and the mixture stirred at room temperature for 10minutes. It was then concentrated and the residue recrystallised fromdiisopropyl ether/ethyl acetate.

Yield: 1.8 g=74.8% of theory

mp: 51° C.

EXAMPLE 4.4

1-(4-Chloro-5-difluoromethoxy-1-methyl-3-pyrazolyl)-5-methyl-4-pyrazolecarbonitrile

0.57 g (2.25 mmol)1-(5-Difluoromethoxy-1-methyl-3-pyrazolyl)-5-methyl-4-pyrazolecarbonitrilewas dissolved in 30 ml methylene chloride and at room temperature wastreated with 0.30 g (2.25 mmol) sulfuryl chloride. The mixture wasstirred for one hour and then concentrated.

Yield: 0.65 g=99.8% of theory

mp: 69°-70° C.

Preparation of the starting materials

1.1-(5-Difluoromethoxy-1-methyl-3-pyrazolyl)-5-methyl-4-pyrazolecarbonitrile

A mixture of 0.79 g (2.91 mmol)1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)-5-methyl-4-pyrazolecarboxamide,0.46 g (5.85 mmol) pyridine and 20 ml 1,4-dioxane was cooled to 5° C.and 0.74 g (3.51 mmol) trifluoroacetic anhydride was added dropwise. Themixture was stirred for 3 hours at room temperature. It was then addedto 100 ml water and extracted 4 times with ethyl acetate. The organicphase was dried over magnesium sulfate and concentrated.

Yield: 0.74=99.8% of theory

mp: 106°-107° C.

2.1-(5-Difluoromethoxy-1-methyl-3-pyrazolyl)-5-methyl-4-pyrazolecarboxamide

0.98 g (3.38 mmol)1-(5-Difluoromethoxy-1-methyl-3-pyrazolyl)-5-methyl-4-pyrazolecarbonylchloride was dissolved in 20 ml tetrahydrofuran and 50 ml aqueousammonia (33%) was added with stirring. After stirring for 3 hours atroom temperature, the mixture was concentrated to half and acidifiedwith dilute hydrochloric acid. The precipitate was suction filtered off,washed with a small amount of water and dried.

Yield: 0.27 g=73% of theory

mp: 116°-118° C.

3.1-(5-Difluoromethoxy-1-methyl-3-pyrazolyl)-5-methyl-4-pyrazolecarbonylchloride

0.2 g (3.8 mmol)1-(5-Difluoromethoxy-1-methyl-3-pyrazolyl)-5-methyl-4-pyrazolecarboxylicacid was suspended in 30 ml 1,2-dichloroethane and 1.19 g (10.0 mmol)thionyl chloride was added at room temperature, dropwise. The mixturewas heated for 1 hour under reflux and concentrated.

Yield: 0.98 g=100% of theory

4.1-(5-Difluoromethoxy-1-methyl-3-pyrazolyl)-5-methyl-4-pyrazolecarboxylicacid

A mixture of 1.25 g (4.16 mmol) Ethyl1-(5-difluoro-methoxy-1-methyl-3-pyrazolyl)-5-methyl-4-pyrazole-carboxylate,20 ml ethanol and 0.97 ml aqueous sodium hydroxide (45%) was stirred for1 hour at 80° C. The reaction solution was concentrated to a half andacidified with hydrochloric acid (37%). The precipitate was suctionfiltered off, washed with water and dried.

Yield: 1.05 g=93% of theory

mp: 205°-207° C.

5. Ethyl1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)-5-methyl-4-pyrazolecarboxylate

3.0 g (16.8 mmol) 5-Difluoromethoxy-3-hydrazino-1-methyl-pyrazole wasadded to 25 ml ethanol and treated dropwise with 2.96 g (16.0 mmol)ethyl dimethylaminomethylenacetate dissolved in 25 ml ethanol. Themixture was heated under reflux for 2 hours. After cooling theprecipitate was suction filtered off.

Yield: 2.52 g=53% of theory

mp: 100° C.

Further starting materials were prepared as follows:

1. 1,1,7-Trichloro-1-hepten-3-one

100 g (0.62 mol) 5-Chlorovaleroyl chloride was added dropwise to 78.53 g(0.589 mmol) aluminium chloride in 150 ml methylene chloride at roomtemperature. After stirring for 1 hour, 45 ml (0.558 mol)1,1-dichloroethylene in 25 ml methylene chloride was added dropwise.Under ice-cooling 100 ml water was added dropwise and solid materialsuction filtered on Celite. The filtrate was washed with water and theorganic phase dried and concentrated. The residue was distilled in arotary evaporator.

Yield: 112.76 g=93.8% of theory.

b.p.: 125° C./0.4 mbar

2. 2-Hydrazino-4,5,6,7-tetrahydropyrazolo 1,5-a!pyridine

261.9 ml (5.4 mol) Hydrazine hydrate was added dropwise to 116.6 g (0.54mol) 1,1,7-trichloro-1-hepten-3-one in 2000 ml 2-propanol at -2° C.(acetone/dry-ice). After stirring for 12 hours at room temperature 60.6g (1,08 mmol) potassium hydroxide was added and the mixture heated for 5hours under reflux. The reaction mixture was evaporated to dryness andthe residue treated with 100 ml water and 100 ml brine. It was extracted9 times with ethyl acetate and the and the organic phase washed withbrine, dried over sodium sulfate and concentrated.

Yield: 29.29 g=35.6% of theory.

Yellow oil

3. 5-Amino-4-cyano-1-(1-methyl-5-methylmercapto-3-Pyrazolyl)pyrazole

A mixture of 2.0 g (13.1 mmol)3-Hydrazino-1-methyl-5-methylmercaptopyrazole and 1.8 g (14.4 mmol)ethoxymethylenemalononitrile in 25 ml ethanol was stirred for 30 minutesat room temperature and heated at boiling point for 3 hours. Thereaction mixture was concentrated and the residue purified by silica gelchromatography (hexane/ethyl acetate 1:1).

Yield 2.8 g=91% of theory.

mp: 165°-166° C.

4. 3-Hydrazino-1-methyl-5-methylmercaptopyrazole

1.1 g (15.8 mmol) sodium nitrite in 4 ml water was added dropwise to 1.9g (13.1 mmol) 3-amino-1-methyl-5-methyl-mercaptopyrazole in 28 mlconcentrated hydrochloric acid at 0° C. and the mixture stirred for 2hours at 0° C. Then, at -30° C., a solution of 7.4 g (32.8 mmol) SnCl₂.2H₂ O in 5.5 ml concentrated hydrochloric acid was added dropwise andthe mixture stirred for 3 hours at this temperature. The reactionmixture was then made basic with 32% caustic soda and extracted withmethylene chloride. The organic phase was dried over sodium sulfate andconcentrated. 2.0 g of product was obtained which was used withoutfurther purification.

5. 3-Amino-1-methyl-5-methylmercaptopyrazole

5.55 g (33.0 mmol) 3-amino-4-cyano-1-methyl-5-methyl-mercaptopyrazoleheated with 50 ml 32% caustic soda at boiling for 24 hours. The reactionmixture was cooled, made slightly acidic with aqueous sodium hydrogenphosphate, heated for 8 hours at 50° C. and extracted with ethylacetate. The organic phase was dried over sodium sulfate, concentratedand the residue purified by silica gel chromatography (hexane/ethylacetate 1:1).

Yield: 19 g=398% of theory.

mp: 164°-166° C.

6. 3-Amino-4-cyano-1-methyl-5-methylmercaptopyrazole

9.63 g (56.6 mmol) Bis(methylmercapto)methylene!-malononitrile wassuspended in 50 ml water and treated with 3.7 ml (67.9 mmol)methylhydrazine. The mixture was heated at boiling for 1 hour, thereaction solution cooled, the precipitate suction filtered andrecrystallised from ethanol.

Yield: 6.5 g=68.% of theory.

mp: 120°-121° C.

7. 5-Amino-1-(4,5,6,7-tetrahydropyrazolo-1,5-a!pyridin-2-yl)-4-pyrazolecarboxylic acid and2-hydrazino-4,5,6,7-tetrahydro-pyrazolo 1,5-a!pyridine

These were prepared according to known methods as follows:

a) 2-Amino-4,5,6,7-tetrahydropyrazolo 1,5-a!pyridine

A solution of 8.19 g (146 mmol) potassium hydroxide in 122 ml water and122 ml ethanol was added to 19.19 g (292 mmol) hydroxylaminehydrochloride in 200 ml ethanol. The mixture was stirred for 15 minutes,12.5 g (58 mmol) 2-(2,5-dimethyl-1-pyrrolyl)-4,5,6-7-tetrahydro-pyrazolo1,5-a!pyridine added and the mixture heated under reflux for 30 hours.After distilling the ethanol, the mixture was treated with ethylacetate, solid material filtered off, the aqueous phase saturated withsodium chloride and extracted with ethyl acetate. The organic phase waswashed with saturated aqueous sodium chloride, dried over sodium sulfateand concentrated. The crude product was purified by silica gelchromatography (ethyl acetate/methanol).

Yield: 6.12 g=77% of theory

¹ H NMR (CDCl₃, 300 MHz): δ=1.75-1.85 (m,2H), 1.95-2,05(m,2H)2.68(t,2H,J=7.5 Hz), 3.5(s(wide),2H), 3.92(t,2H,J=7.5 Hz), 5.33(s,1H)

b) 2-(2,5-Dimethyl-1-pyrrolyl)-4,5,6,7-tetrahydro-pyrazolo1,5-a!pyridine

16 g (92 mmol) diethyl azodicarboxylate was added dropwise to 19.7 g (84mmol) 3(5)-(4-hydroxybutyl)-5(3)-(2,5-dimethyl-1-pyrrolyl)pyrazole and22.1 g (84 mmol) triphenylphosphine in 300 ml tetrahydrofuran under icecooling. The mixture was stirred for 4 hours at room temperature. It wasthen concentrated and the residue purified by silica gel chromatography(hexane/ethyl acetate).

Yield: 14.27 g=79% of theory

n_(D) ²⁰ :1.5630

c) 3(5)-(4-Hydroxybutyl)-5(3)-(2,5-dimethyl-1-pyrrolyl)pyrazole

A mixture of 18 g (116 mmol) 3(5)-amino-5(3)-(hydroxy-butyl)pyrazole,14.6 g (128 mmol) 2,5-hexanedione and 3.2 ml acetic acid in 100 mltoluene was heated under reflux with removal of water for 8 hours. Theresulting precipitate was suction filtered, washed with toluene anddried.

Yield: 19.7 g=72% of theory

mp: 147°-148° C.

d) 3(5)-Amino-5(3)-(hydroxybutyl)pyrazole

4,8 ml Hydrazine monohydrate was added to a solution of 12.3 g (0.1 mol)tetrahydro-2H-pyran-2-ylidenacetonitrile in 100 ml toluene at roomtemperature and the mixture heated under reflux for 5 hours. A darkyellow oil separated. The reaction mixture was concentrated and theresidue purified by silica gel chromatography (ethyl acetate/methanol).

Yield: 11 g=71% of theory

In a similar manner to that described in the previous Examples, thefollowing compounds were prepared.

    __________________________________________________________________________    General formula                                                                ##STR74##                                                                    Compound                           Physical                                                                              Constant                           No.     R.sup.5                                                                              R.sup.6             mp  °C.!                                                                       n.sub.D.sup.20                     __________________________________________________________________________    1.3     H      H                   80-82                                      1.4     CN     H                   120-121                                    1.5     H      NHCOC.sub.2 H.sub.5 149-151                                    1.6     CN     NHCH.sub.3          174-175                                    1.7     CN     N(CH.sub.3)2        138-139                                    1.8     CN     N(C.sub.2 H.sub.5).sub.2    1,5432                             1.9     CN     NHCOCH.sub.2 Cl     209-211                                    1.10    CN     N(CH.sub.3)COCH.sub.2 Cl                                                                          109-110                                    1.11    CN                                                                                    ##STR75##          131-132                                    1.12    NO.sub.2                                                                             N(C.sub.2 H.sub.5).sub.2                                                                          55-57                                      1.13    NO.sub.2                                                                             NHCH.sub.3          184-185                                    1.14    CN     Cl                  176-177                                    1.15    CN     Br                  196-198                                    1.16    NO.sub.2                                                                             Cl                                                             1.17    NO.sub.2                                                                             Br                                                             1.18    CN     CH.sub.3            168-171                                    1.19    CN     C.sub.2 H.sub.5                                                1.20    CN     C.sub.3 H.sub.7                                                1.21    NO.sub.2                                                                             CH.sub.3                                                       1.22    NO.sub.2                                                                             C.sub.2 H.sub.5                                                1.23    NO.sub.2                                                                             C.sub.3 H.sub.7                                                1.24    CN     OCH.sub.3                                                      1.25    CN     OC.sub.2 H.sub.5                                               1.26    NO.sub.2                                                                             OCH.sub.3                                                      1.27    NO.sub.2                                                                             OC.sub.2 H.sub.5                                               1.28    NO.sub.2                                                                             OCH(CH.sub.3)CO.sub.2 CH.sub.3                                 1.29    NO.sub.2                                                                             OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                          1.30    NO.sub.2                                                                             SCH.sub.3                                                      1.31    NO.sub.2                                                                             SOCH.sub.3                                                     1.32    NO.sub.2                                                                             SO.sub.2 CH.sub.3                                              1.33    NO.sub.2                                                                             SC.sub.2 H.sub.5                                               1.34    CN     SCH.sub.2 COOEt                                                1.35    NO.sub.2                                                                             SCH.sub.2 COOEt                                                1.36    CN     NHCO(CH.sub.2).sub.2 Cl                                                                           149-150                                    1.37    CN     NHCO(CH.sub.2).sub.3 Cl                                                                           119-121                                    __________________________________________________________________________    General Formula                                                                ##STR76##                                                                    Compound                                Physical                                                                           Constant                         No.   R.sup.1                                                                          R.sup.2                                                                            R.sup.3                                                                         R.sup.5                                                                           R.sup.6             mp °C.!                                                                     n.sub.D.sup.20                   __________________________________________________________________________    2.2   CH.sub.3                                                                         OCH.sub.3                                                                          Cl                                                                              NO.sub.2                                                                          NHCOCH.sub.3        46-48                                 2.3   CH.sub.3                                                                         OCHF.sub.2                                                                         H H   NHCOCF.sub.3        67-70                                 2.4   CH.sub.3                                                                         OCHF.sub.2                                                                         H H   N(CH.sub.3)COCH.sub.3                                                                              66                                   2.5   CH.sub.3                                                                         OCHF.sub.2                                                                         H NO.sub.2                                                                          NHCOCH.sub.3        115-116                               2.6   CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              H   NHCOCH.sub.3        106                                   2.7   CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              H   NHCOC.sub.2 H.sub.5 114-119                               2.8   CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              H   NHCOC.sub.3 H.sub.7 80-84                                 2.9   CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              H   NHCOCH.sub.2 Cl     111-115                               2.10  CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              H                                                                                  ##STR77##          152-156                               2.11  CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              NO.sub.2                                                                          NHCOC.sub.2 H.sub.5 109-110                               2.12  CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              NO.sub.2                                                                          NHCOC.sub.3 H.sub.7 92-96                                 2.13  CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              NO.sub.2                                                                          NHCOCH.sub.2 Cl     118-120                               2.14  CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              NO.sub.2                                                                           ##STR78##          194-196                               2.15  CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              NO.sub.2                                                                          NHCH.sub.3          102-105                               2.16  CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              NO.sub.2                                                                          N(CH.sub.3).sub.2        1.5564                           2.17  (CH.sub.2).sub.4                                                                      Cl                                                                              NO.sub.2                                                                          NHCOCH.sub.3        162(dec.)                             2.18  (CH.sub.2).sub.4                                                                      Cl                                                                              NO.sub.2                                                                          NHCOC.sub.3 H.sub.7 58-61                                 2.19  (CH.sub.2).sub.4                                                                      Cl                                                                              NO.sub.2                                                                           ##STR79##          168(dec.)                             2.20  CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              H   NHCO.sub.2 C.sub.2 H.sub.5                                                                        144-146                               2.21  CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              H   NHCONH.sub.2                                              2.22  CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              H   NHCONHCH.sub.3                                            2.23  CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              H   NHCON(CH.sub.3).sub.2                                     2.24  CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              NO.sub.2                                                                          NHCO.sub.2 C.sub.2 H.sub.5                                                                             1.5337                           2.25  CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              NO.sub.2                                                                          NHCONH.sub.2                                              2.26  CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              NO.sub.2                                                                          NHCONHCH.sub.3                                            2.27  CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              NO.sub.2                                                                          NHCON(CH.sub.3).sub.2                                     2.28  (CH.sub.2).sub.4                                                                      Cl                                                                              NO.sub.2                                                                          NHCO.sub.2 C.sub.2 H.sub.5                                2.29  (CH.sub.2).sub.4                                                                      Cl                                                                              NO.sub.2                                                                          NHCONH.sub.2                                              2.30  (CH.sub.2).sub.4                                                                      Cl                                                                              NO.sub.2                                                                          NHCONHCH.sub.3                                            2.31  (CH.sub.2).sub.4                                                                      Cl                                                                              NO.sub.2                                                                          NHCON(CH.sub.3).sub.2                                     2.32  CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              NO.sub.2                                                                          OCH.sub.3                                                 2.33  CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              NO.sub.2                                                                          OC.sub.2 H.sub.5                                          2.34  CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              NO.sub.2                                                                          OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                     2.35  CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              NO.sub.2                                                                          SCH.sub.3                                                 2.36  CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              NO.sub.2                                                                          SOCH.sub.3                                                2.37  CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              NO.sub.2                                                                          SO.sub.2 CH.sub.3                                         2.38  (CH.sub.2).sub.4                                                                      Cl                                                                              NO.sub.2                                                                          NHCOCF.sub.3        56-60                                 2.39  CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              NO.sub.2                                                                           ##STR80##          44-48                                 2.40  CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              NO.sub.2                                                                           ##STR81##               1.5725                           2.41  CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              NO.sub.2                                                                           ##STR82##          47-51                                 2.42  CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              H                                                                                  ##STR83##          122-124                               __________________________________________________________________________    General formula                                                                ##STR84##                                                                    Example                           Physical                                                                              Constant                            No.     R.sup.3                                                                            R.sup.6              mp  °C.!                                                                       n.sub.D                             __________________________________________________________________________    2.43    Cl   CH.sub.2 OCH.sub.2 CO.sub.2 Me                                                                             1.51438                             2.44    Cl                                                                                  ##STR85##                   1.50800                             2.45    Cl                                                                                  ##STR86##                   1.51254                             2.46    Cl   CH.sub.2 SCH.sub.3           1.54268                             2.47    Cl   CH.sub.2 SEt                 1.53566                             2.48    Cl                                                                                  ##STR87##           74                                          2.49    Cl   CH.sub.2 SCH.sub.2 CO.sub.2 Et                                                                             1.52740                             2.50    Cl   CH.sub.2 NH.sub.2            1.53932                             2.51    Cl   CH.sub.2 NHMe                                                    2.52    Cl   CH.sub.2 NHEt                                                    2.53    Cl                                                                                  ##STR88##                   1.51362                             2.54    Cl   CH.sub.2 NMe.sub.2                                               2.55    Cl   CH.sub.2 NEt.sub.2                                               2.56    Cl   CH.sub.2 N prop.sub.2                                            2.57    Cl   CH.sub.2 OCH.sub.2 Cl                                            2.58    Cl   CH.sub.2 OCH.sub.2 CN                                            2.59    Cl   CH.sub.2 OCH.sub.2CCH                                            2.60    Cl                                                                                  ##STR89##                                                       2.61    Cl                                                                                  ##STR90##                                                       2.62    Cl   CH.sub.2 OCH.sub.2 CO.sub.2 Et                                   2.63    Cl                                                                                  ##STR91##                                                       2.64    Cl                                                                                  ##STR92##                                                       4.6     Cl   CH.sub.3             69-70                                       4.7     Br   CH.sub.3             76-78                                       4.8     Cl   CF.sub.3             90-93                                       4.9     Br   CF.sub.3             83-86                                       4.10    Cl   C.sub.2 H.sub.5      74-76                                       4.11    Cl   C(CH.sub.3).sub.3    57-60                                       4.12    Cl   CH.sub.2 OCH.sub.3           1.50852 (20° C.)             4.13    Br   CH.sub.2 OCH.sub.3           1.52580                             4.14    Cl                                                                                  ##STR93##           118-122                                     4.15    Cl   CH.sub.2 OH          64                                          4.16    Cl   CH.sub.2 Cl          54                                          4.17    Cl   CH.sub.2 Br          52                                          4.18    Cl   CH.sub.2 OEt         67                                          4.19    Cl   CH.sub.2 Oprop       48                                          4.20    Cl                                                                                  ##STR94##                   1.50778 (20° C.)             4.21    Cl   CH.sub.2 O(CH.sub.2).sub.3 CH.sub.3                                                                        1.50450 (20° C.).            __________________________________________________________________________    General formula                                                                ##STR95##                                                                    Example                            Physical                                                                             Constant                            No.    R.sup.1                                                                              R.sup.2                                                                              R.sup.3                                                                              R.sup.6                                                                              mp.:  °C.!                                                                    n.sub.D                             __________________________________________________________________________    4.22   (CH.sub.2).sub.4                                                                            Br     Br     204-205                                    4.23   CH.sub.3                                                                             OCHF.sub.2                                                                           Cl     Br     71-74                                      4.24   CH.sub.3                                                                             OCHF.sub.2                                                                           Cl     Cl            1.54046 (20.2° C.)           4.25   CH.sub.3                                                                             OCHF.sub.2                                                                           Br     Br     96-97                                      __________________________________________________________________________    General formula                                                                ##STR96##                                                                    Example                           Physical                                                                              Constant                            No.     R.sup.3                                                                            R.sup.6              mp:  °C.!                                                                      n.sub.D                             __________________________________________________________________________    4.26    Cl   CF.sub.3             109-110                                     4.27    Cl   C.sub.2 H.sub.5      130-131                                     4.28    Cl   C.sub.2 F.sub.5      135.5-136                                   4.29    Cl   C.sub.3 H.sub.7      62-63                                       4.30    Cl   CH(CH.sub.3).sub.2   107-108                                     4.31    Cl   Ph                   153-154                                     4.32    Cl   CH.sub.2 OCH.sub.3   84-85                                       4.33    Br   CH.sub.2 OCH.sub.3   80-83                                       4.34    Cl   CH.sub.2 OC.sub.2 H.sub.5                                                                          73-74                                       4.35    Cl   CH.sub.2 OC.sub.3 H.sub.7                                                                          88-89                                       4.36    Cl   CH.sub.2 OCH(CH.sub.3).sub.2 1.5440 (20.1° C.)            4.37    Cl   CH.sub.2 OH          106-107                                     4.38    Cl   CH.sub.2 Br          128-129                                     4.39    Cl   CH.sub.2 OCH.sub.2 CCH       1.5591 (21,2° C.)            4.40    Cl   CH.sub.2 OCH.sub.2 CHCH.sub.2                                                                      100.5-102                                   4.41    Cl   CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3                                                                      1.5492 (20,2° C.)            4.42    Cl   CH.sub.2 OCOCH.sub.3 102.5-103                                   4.43    Cl   CH.sub.2 OCH.sub.2 COOH                                                                            108-110                                     4.44    Cl   CH.sub.2 OCH.sub.2 COOCH.sub.3                                                                             1.5376 (20° C.)              4.45    Cl                                                                                  ##STR97##                   1.5462 (20.1° C.)            4.46    Cl                                                                                  ##STR98##                   1.5424 (21° C.)              4.47    Cl                                                                                  ##STR99##                   1.5500 (20° C.)              4.48    Cl                                                                                  ##STR100##                  1.5481 (20,2° C.)            4.49    Cl   CH.sub.2 N(C.sub.2 H.sub.5).sub.2                                                                          1.5377 (20° C.)              4.50    Cl   CH.sub.2 SCH.sub.3   100-101                                     4.51    Cl   CH.sub.2 SO.sub.2 CH.sub.3                                                                         139.5-141                                   4.52    Cl   CH.sub.2 SOCH.sub.3          1.5716 (20° C.)              4.53    Cl   CH.sub.2 SCOOH       120                                         4.54    Cl   CH.sub.2 SCH.sub.2 COOC.sub.2 H.sub.5                                                                      1.5641 (20° C.)              4.55    Cl   COOH                 184                                         4.56    Cl   CON(C.sub.2 H.sub.5).sub.2                                                                         126.5-128                                   General formula                                                                ##STR101##                                                                   4.57    Cl   NHC.sub.3 H.sub.7    137                                         4.58    Cl   NHCH(CH.sub.3).sub.2 114                                         4.59    Cl   NH(CH.sub.2CH═CH.sub.2)                                                                        125                                         4.60    Cl   NHC.sub.4 H.sub.9    118                                         4.61    Cl   NH CH(CH.sub.3)CH.sub.2 CH.sub.3 !                                                                 106                                         4.62    Cl   NH CH(CH.sub.3)CH(CH.sub.3).sub.2 !                                                                89-92                                       4.63    Cl   NHCH.sub.2 CH.sub.2 OCH.sub.3                                                                      129                                         4.64    Cl   NHCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                               111-112                                     4.65    Cl   NHCH(CH.sub.3)CH.sub.2 OCH.sub.3                                                                   105-106                                     4.66    Cl   NHCH.sub.2 CH.sub.2 N(CH.sub.3).sub.2                                                              131-132                                     4.67    Cl   N(CH.sub.3)CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2                                                             1.5621 (20° C.)              4.68    Cl   NHCH.sub.2 Ph        116                                         4.69    Cl                                                                                  ##STR102##          122-123                                     4.70    Br   N(CH.sub.3)C.sub.2 H.sub.5                                                                         74-76                                       4.71    Br   N(CH.sub.3)C.sub.3 H.sub.7                                                                         93-95                                       4.72    Cl   N(CH.sub.3)CH(CH.sub.3).sub.2                                                                       74                                         4.73    Cl   N(CH.sub.3)CH.sub.2-CCH                                                                             91                                         4.74    Br   N(CH.sub.3)CH.sub.2-CCH                                                                            112-114                                     4.75    Cl   N(C.sub.2 H.sub.5)CH.sub.2-CCH.sub.2                                                                75                                         4.76    Cl   N(C.sub.2 H.sub.5)CH.sub.2-CCH                                                                             1.5642 (21.5° C.)            4.77    Cl   N(C.sub.3 H.sub.7).sub.2     1.5468 (23.8° C.)            4.78    Cl                                                                                  ##STR103##          156                                         4.79    Cl                                                                                  ##STR104##           84                                         4.80    Cl                                                                                  ##STR105##          107                                         4.81    Cl   CN                   123                                         4.82    Cl   N(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2                                                      1.5559 (20° C.)              4.83    Cl   N(CH.sub.2CH═CH.sub.2).sub.2                                                                    79                                         4.84    Cl                                                                                  ##STR106##          145                                         4.85    Cl   NHCH.sub.2CCH        145                                         4.86    Cl   NHCH(C.sub.2 H.sub.5).sub.2                                                                         96                                         4.87    Cl                                                                                  ##STR107##          139-142                                     4.88    Cl                                                                                  ##STR108##          141                                         4.89    Cl   NHCH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2                                                       78-80                                       4.90    Cl   NHCH.sub.2 CH.sub.2 OH                                                                             138                                         4.91    Cl   NHCH.sub.2 CH.sub.2 OCOCH.sub.3                                                                     99                                         4.92    Cl   NHCH.sub.2 CH.sub.2 Cl                                                                             158                                         4.93    Cl   NH(CH.sub.2).sub.3 OCH.sub.3                                                                       112                                         4.94    Cl   NHCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                          82-84                                       4.95    Cl   NHCH.sub.2 CH(OCH.sub.3).sub.2                                                                     127-129                                     4.96    Cl   NHCH(CH.sub.3)CH(OCH.sub.3).sub.2                                                                  151                                         4.97    Cl   NHCH.sub.2 CH(OC.sub.2 H.sub.5).sub.2                                                              111-113                                     4.98    Cl                                                                                  ##STR109##          115-117                                     4.99    Cl                                                                                  ##STR110##          121-123                                     4.100   Cl                                                                                  ##STR111##          149-151                                     4.101   Cl                                                                                  ##STR112##          114.5-117                                   4.102   Cl   NHCH.sub.2 CH.sub.2 SC.sub.2 H.sub.5                                                               113-115                                     4.103   Cl                                                                                  ##STR113##          170                                         4.104   Cl                                                                                  ##STR114##          129-131                                     4.105   Cl   NHCH.sub.2 COOC.sub.2 H.sub.5                                                                      162                                         4.106   Cl                                                                                  ##STR115##                                                      4.107   Cl                                                                                  ##STR116##                                                      4.108   Cl                                                                                  ##STR117##                                                      4.109   Cl                                                                                  ##STR118##                                                      4.110   Cl                                                                                  ##STR119##                                                      4.111   Cl                                                                                  ##STR120##                                                      4.112   Cl                                                                                  ##STR121##                                                      General formula                                                                ##STR122##                                                                   4.113   Cl   NHC.sub.3 H.sub.7    80                                          4.114   Cl                                                                                  ##STR123##          77                                          4.115   Cl   NH(CH.sub.2).sub.2 OCH.sub.3                                                                      78-79                                        4.116   Cl   N(CH.sub.3)C.sub.2 H.sub.5  1.52076 (20° C.)              4.117   Cl   N(C.sub.2 H.sub.5).sub.2    1.49924 (20° C.)              4.118   Cl   N(CH.sub.3)CH(CH.sub.3).sub.2                                                                             1.51528 (20° C.)              4.119   Br   N(CH.sub.3)CH(CH.sub.3).sub.2                                                                             1.51258 (20,3° C.)            4.120   Cl   N(C.sub.2 H.sub.5)CH(CH.sub.3).sub.2                                                               52                                          4.121   Cl   N(C.sub.3 H.sub.7).sub.2    1.49338 (20° C.)              4.122   Cl                                                                                  ##STR124##         100-102                                      4.123   Br                                                                                  ##STR125##         70-72                                        4.124   Cl                                                                                  ##STR126##                 1.53388 (21.6° C.)            __________________________________________________________________________    General formula                                                                ##STR127##                                                                   Example                              Physical                                                                            Constant                           No.  R.sup.1                                                                           R.sup.2                                                                             R.sup.3                                                                         R.sup.6             mp:  °C.!                                                                    n.sub.D                            __________________________________________________________________________    4.125                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              NHC.sub.2 H.sub.5   136                                      4.126                                                                              CH.sub.3                                                                          OCHF.sub.2                                                                          Cl                                                                              NHCH.sub.3          147-148                                  4.127                                                                              CH.sub.3                                                                          OCHF.sub.2                                                                          Br                                                                              NHCH.sub.3          150-152                                  4.128                                                                              CH.sub.3                                                                          OCHF.sub.2                                                                          Br                                                                              NHC.sub.2 H.sub.5   96                                       4.129                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                               ##STR128##         133                                      4.130                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              NHCH.sub.2 CN       183                                      4.131                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              NHCH.sub.2CCCH.sub.3                                                                              171.5-173.5                              4.132                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              NHCH.sub.2 CCCH.sub.3                                        4.133                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              NHCH.sub.2CCCC.sub.2 H.sub.5                                 4.134                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              NHCH.sub.2CCCH.sub.2OCH.sub.3                                General formula                                                                ##STR129##                                                                   4.135                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(CH.sub.3)C.sub.2 H.sub.5                                                                         69                                      4.136                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(CH.sub.3)C.sub.3 H.sub.7                                                                         89                                      4.137                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(CH.sub.3)C.sub.4 H.sub.9                                                                         72                                      4.138                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(CH.sub.3)CH(CH.sub.3)C.sub.2 H.sub.5                                                             68                                      4.139                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(CH.sub.3)CH(CH.sub.3)CH(CH.sub.3).sub.2                                                          70                                      4.140                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(CH.sub.3)CH.sub.2 CH.sub.2 OCH.sub.3                                                             80                                      4.141                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(C.sub.2 H.sub.5)C.sub.3 H.sub.7                                                                  92                                      4.142                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(C.sub.2 H.sub.5)C.sub.4 H.sub.9                                                                       1.5471 (22.9° C.)           4.143                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(C.sub.2 H.sub.5)CH(CH.sub.3)C.sub.2 H.sub.5                                                     115                                      4.144                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(C.sub.2 H.sub.5)CH(CH.sub.3)CH(CH.sub.3).sub.2                                                  130-133                                  4.145                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2 OCH.sub.3                                                      58                                      4.146                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(C.sub.2 H.sub.5)CH.sub.2 Ph                                                                     110                                      4.147                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(CH.sub.3)CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                           1.5559 (20° C.)             4.148                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                    1.5484 (20° C.)             4.149                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(C.sub.3 H.sub.7)CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                    1.5452 (20° C.)             4.150                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(CH.sub.2CCH)CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                        1.55688 (20° C.)            4.151                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(CH.sub.3)CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                               1.55644 (20° C.)            4.152                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(C.sub.2 H.sub.5)CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                  94-95                                    4.153                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(CH.sub.2CCH)CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                      124-126                                  4.154                                                                              CH.sub.3                                                                          OCHF.sub.2                                                                          Cl                                                                              N(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2 OCH.sub.3                                                           1.51744 (19.9° C.)          4.155                                                                              CH.sub.3                                                                          OCHF.sub.2                                                                          Cl                                                                              N(CH.sub.2CCH)CH.sub.2 CH.sub.2 OCH.sub.3                                                               1.51376 (20° C.)            4.156                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              NH(CH.sub.2CCH)     145                                      4.157                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(CH(CH.sub.3)C.sub.2 H.sub.5)CH.sub.2CCH                                                         142                                      4.158                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                               ##STR130##         108                                      4.159                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(C.sub.2 H.sub.5)CH(CH.sub.3)CH.sub.3                                                            106                                      4.160                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(C.sub.2 H.sub.5)CH(CH.sub.3).sub.2                                                              106                                      4.161                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(CH.sub.2CCH)CH(CH.sub.3)C.sub.2 H.sub.5                                                         142                                      4.162                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(CH.sub.3)CH.sub.2 Ph                                                                            108                                      4.163                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(CH.sub.3)CH(C.sub.2 H.sub.5).sub.2                                                              110                                      4.164                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(CH.sub.3)CH.sub.2 CH(OCH.sub.3).sub.2                                                            71                                      4.165                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(C.sub.2 H.sub.5)CH.sub.2 CH(OCH.sub.3).sub.2                                                          1.5459 (20° C.)             4.166                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(CH.sub.2CCH)CH.sub.2 CH(OCH.sub.3).sub.2                                                        111-113                                  4.167                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                               ##STR131##         97-99                                    4.168                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                               ##STR132##         169-171                                  4.169                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                               ##STR133##         140-142                                  4.170                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(CH.sub.3)CH.sub.2 CH.sub.2 SC.sub.2 H.sub.5                                                           1.5855 (22.4° C.)           4.171                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(CH.sub.3)CH.sub.2CCCH.sub.3                                4.172                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(CH.sub.3)CH.sub.2CCC.sub.2 H.sub.5                         4.173                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                              N(CH.sub.3)CH.sub.2CCCH.sub.2OCH.sub.3                       4.174                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                               ##STR134##                                                  4.175                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                               ##STR135##                                                  4.176                                                                              (CH.sub.2).sub.4                                                                        Cl                                                                               ##STR136##                                                  __________________________________________________________________________    General formula                                                                ##STR137##                                                                   Example                           Physical                                                                              Constant                            No.     R.sup.3                                                                            R.sup.6              mp:  °C.!                                                                      n.sub.D                             __________________________________________________________________________    4.177   Br   N(C.sub.2 H.sub.5).sub.2                                                                           71-72                                       4.178   Cl   N(CH.sub.2CCH).sub.2         1,5739 (22.8° C.)            4.179   Cl   N(CH.sub.2 CO.sub.2 C.sub.2 H.sub.5).sub.2                                                                 1.5427 (20° C.)              4.180   Cl                                                                                  ##STR138##          108                                         4.181   Cl   N(CH.sub.2CCCH.sub.3).sub.2                                      4.182   Cl   N(CH.sub.2CCC.sub.2 H.sub.5).sub.2                               4.183   Cl   N(CH.sub.2CCCCH.sub.2 OCH.sub.3).sub.2                           General formula                                                                ##STR139##                                                                   4.184   Cl   NHCOCH.sub.3         123                                         4.185   Cl   NHCOCF.sub.3         178                                         4.186   Cl   NHCOCCl.sub.3        224                                         4.187   Cl   NHCOC.sub.2 H.sub.5  162                                         4.188   Cl   NHCOC.sub.3 H.sub.7  152                                         4.189   Br   NHCOC.sub.3 H.sub.7  148-150                                     4.190   Cl                                                                                  ##STR140##          171                                         4.191   Cl   NHCOC.sub.4 H.sub.9  103                                         4.192   Cl                                                                                  ##STR141##          252                                         4.193   Cl   NHCOCH.sub.2 OCH.sub.3                                                                             201-203                                     4.194   Cl                                                                                  ##STR142##          185-187                                     4.195   Cl                                                                                  ##STR143##          165                                         4.196   Cl                                                                                  ##STR144##          151                                         4.197   Cl                                                                                  ##STR145##           75                                         4.198   Cl                                                                                  ##STR146##          185                                         4.199   Cl   NHCON(CH.sub.3).sub.2                                                                              168                                         4.200   Cl   NHCSN(CH.sub.3).sub.2                                                                              170                                         4.201   Cl   NHCON(CH.sub.3)Ph    62-64                                       General formula                                                                ##STR147##                                                                   4.202   Cl                                                                                  ##STR148##          125                                         4.203   Cl   NHCH.sub.2 CO.sub.2 Et                                                                             107-109                                     4.204   Cl                                                                                  ##STR149##          111-113                                     4.205   Cl   N(Et)COCH.sub.3      78-80                                       4.206   Cl   N(Et)COCH.sub.2 Cl           1.53412                             4.207   Cl                                                                                  ##STR150##          85-87                                       4.208   Cl   N(Et)COEt                    1.51132                             4.209   Cl                                                                                  ##STR151##                  1.51214                             4.210   Cl                                                                                  ##STR152##                  1.52582                             4.211   Cl   N(CH.sub.2 CO.sub.2 Me)COEt                                                                        87-90                                       4.212   Br   NHCOEt               120-122                                     4.213   Br   NHCOnbutyl           100-104                                     4.214   Br                                                                                  ##STR153##          103                                         4.215   Br   N(COEt).sub.2        105-107                                     4.216   Cl   NHCOCH.sub.3         116-118                                     4.217   Cl   NHCOCH.sub.2 Cl      135-137                                     4.218   Cl   NHCOCF.sub.3         134-137                                     4.219   Cl   NHCOC.sub.2 H.sub.5  126-128                                     4.220   Br   NHCOC.sub.3 H.sub.7  141-144                                     4.221   Cl   NHCOC.sub.3 H.sub.7  140-143                                     4.222   Cl                                                                                  ##STR154##           96-100                                     4.223   Cl   N(COCH.sub.3).sub.2  117-119                                     4.224   Cl   N(COC.sub.2 H.sub.5).sub.2                                                                         93-95                                       4.225   Cl   N(COC.sub.3 H.sub.7).sub.2                                                                         73-76                                       General formula                                                                ##STR155##                                                                   4.226   Cl   N(CH.sub.3)COCH.sub.3                                                                              121                                         4.227   Cl   N(C.sub.2 H.sub.5)COCH.sub.3                                                                        79                                         4.228   Cl   N(C.sub.3 H.sub.7)COCH.sub.3                                                                        85                                         4.229   Cl   (CH.sub.2CCH)COCH.sub.3                                                                             06                                         4.230   Cl   N(CH.sub.2 CH.sub.2 OCH.sub.3)COCH.sub.3                                                           128                                         4.231   Cl   N(CH.sub.2 Ph)COCH.sub.3                                                                           111-113                                     4.232   Cl   N(C.sub.2 H.sub.5)COCH.sub.2 Cl                                                                    98-101                                      4.233   Cl   N(C.sub.3 H.sub.7)COCH.sub.2 Cl                                                                    168                                         4.234   Cl   N(CH.sub.2 CH.sub.2 OCH.sub.3)COCH.sub.2 Cl                                                        107                                         4.235   Cl   N(CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5)COCH.sub.2 Cl                                                         1.54132 (20° C.)             4.236   Cl   N(CH.sub.2 Ph)COCH.sub.2 Cl                                                                        165-168                                     4.237   Cl   N(CH.sub.3)COCF.sub.3                                                                               98                                         4.238   Cl   N(C.sub.2 H.sub.5)COCF.sub.3                                                                       102                                         4.239   Cl   N(CH.sub.2CCH)COCF.sub.3                                                                           137                                         4.240   Cl   N(CH.sub.3)COC.sub.2 H.sub.5                                                                       125-128                                     4.241   Cl   N(C.sub.2 H.sub.5)COC.sub.2 H.sub.5                                                                 83                                         4.242   Cl   N(CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5)COC.sub.2 H.sub.5                                                     1.54132 (20° C.)             4.243   Cl   N(CH.sub.3)COC.sub.3 H.sub.7                                                                        90                                         4.244   Cl   N(C.sub.2 H.sub.5)COC.sub.3 H.sub.7                                                                 72                                         4.245   Br   N(C.sub.2 H.sub.5)COC.sub.3 H.sub.7                                                                103-104                                     4.246   Cl                                                                                  ##STR156##          121                                         4.247   Cl                                                                                  ##STR157##          122                                         4.248   Cl                                                                                  ##STR158##          191                                         4.249   Cl   N(CH.sub.3)COC.sub.4 H.sub.9 1.5427 (23.2° C.)            4.250   Cl   N(C.sub.2 H.sub.5)COC.sub.4 H.sub.9                                                                        1.5386 (23.3° C.)            4.251   Cl   N(COCH.sub.3)CH.sub.2 OCH.sub.3                                                                    109                                         4.252   Cl   N CH(CH.sub.3).sub.2 !COCH.sub.3                                                                   112-114                                     4.253   Cl   N(CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5)COCH.sub.3                                                    100-103                                     4.254   Cl   N CH(CH.sub.3)CH(CH.sub.3).sub.2 !COCH.sub.3                                                        93                                         4.255   Cl   N CH(CH.sub.3).sub.2 !COCH.sub.2 Cl                                                                146-149                                     4.256   Cl   N CH(CH.sub.3)C.sub.2 H.sub.5 !COCH.sub.2 Cl                                                       109-111                                     4.257   Cl   N CH(CH.sub.3)CH.sub.2 OCH.sub.3 !COCH.sub.2 Cl                                                    126                                         4.258   Cl   N(CH.sub.2 CH.sub.2 SC.sub.2 H.sub.5)COCH.sub.3                                                            1.5655 (22.4° C.)            General formula                                                                ##STR159##                                                                   4.259   Cl   N(CH.sub.3)COCH.sub.3                                                                              108-109                                     4.260   Cl   N(CH.sub.3)COCH.sub.2 Cl                                                                           87-90                                       4.261   Cl   N(CH.sub.3)COC.sub.2 H.sub.5                                                                       63-67                                       4.262   Cl   N(C.sub.2 H.sub.5)COCH.sub.3                                                                        77                                         4.263   Br   N(C.sub.2 H.sub.5)COC.sub.3 H.sub.7                                                                75-77                                       4.264   Cl   N(C.sub.3 H.sub.7)COCH.sub.3                                                                       78-80                                       4.265   Br   N(Et)COEt                    1.5168                              4.266   Br                                                                                  ##STR160##                  1.51532                             4.267   Br                                                                                  ##STR161##                  1.53406                             4.268   Br   N(CH.sub.2 CN)COEt   95-98                                       4.269   Br   N(Me)COC.sub.3 H.sub.7       1.55112                             4.270   Br   N(CH.sub.2 OCH.sub.3)COC.sub.3 H.sub.7                                                                     1.53024                             4.271   Br   N(CH.sub.2 CO.sub.2 Et)COC.sub.3 H.sub.7                                                                   1.52918                             General formula                                                                ##STR162##                                                                   4.272   Cl   OCH.sub.3            174-176                                     4.273   Cl   OC.sub.2 H.sub.5     117-118                                     4.274   Br   OC.sub.2 H.sub.5     120-122                                     4.275   Cl   OC.sub.3 H.sub.7     95-96                                       4.276   Cl   OCH.sub.2 CH.sub.2 OCH.sub.3 1.55562 (20° C.)             4.277   Cl   OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3                                                            1.54220 (20° C.)             4.278   Cl   OCH.sub.2CCH         123                                         4.279   Cl   OC.sub.4 H.sub.9     74-76                                       4.280   Cl                                                                                  ##STR163##           99.5-101.5                                 4.281   Cl                                                                                  ##STR164##          102-104                                     4.282   Cl                                                                                  ##STR165##                  1.5575 (21.8° C.)            4.283   Cl                                                                                  ##STR166##                  1.5520 (22° C.)              4.284   Cl                                                                                  ##STR167##                  1.5524 (21.8° C.)            4.285   Cl                                                                                  ##STR168##          67-70                                       4.286   Cl   OCH.sub.2 CH.sub.2 CH(OC.sub.2 H.sub.5).sub.2                                                              1.5306 (20° C.)              4.287   Cl                                                                                  ##STR169##          91-93                                       4.288   Cl                                                                                  ##STR170##                  1.5544 (22.7° C.)            4.289   Cl   SCH.sub.2 COOCH(CH.sub.3).sub.2                                                                    125                                         4.290   Cl                                                                                  ##STR171##                  1.6136 (21.5° C.)            4.291   Cl   SCH.sub.3            128                                         4.292   Cl   SCH.sub.2 CH.sub.3    62                                         4.293   Cl   SCH(CH.sub.3).sub.2          1.5786 (21.8° C.)            4.294   Cl   SCH.sub.2-CCH         94                                         4.295   Cl   SCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                                                                         1.5646 (22.5° C.)            4.296   Cl   SCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                                      1.5602 (21.8° C.)            4.297   Cl   SOCH.sub.3           163                                         4.298   Cl   SO.sub.2 CH.sub.3    229                                         4.299   Cl   OCH.sub.2 CH(CH.sub.3).sub.2                                                                       84-87                                       4.300   Cl   OCH.sub.2 CH(OC.sub.2 H.sub.5).sub.2                                                                       1.5283 (20° C.)              4.301   Cl   O(CH.sub.2).sub.3 OCH.sub.3  1.5482 (20° C.)              4.302   Cl   OCH.sub.2 Ph         120-122                                     4.303   Cl   OCH.sub.2 CH.sub.2 OCH(CH.sub.3).sub.2                                                             67-69                                       4.304   Cl                                                                                  ##STR172##          149-152                                     4.305   Cl   OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                            4.306   Cl   OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                               4.307   Cl                                                                                  ##STR173##                                                      4.308   Cl                                                                                  ##STR174##                                                      4.309   Cl                                                                                  ##STR175##                                                      4.310   Cl                                                                                  ##STR176##                                                      4.311   Cl                                                                                  ##STR177##                                                      __________________________________________________________________________    General formula                                                                ##STR178##                                                                   Example                       Physical  Constant                              No.     R.sup.6               mp:  °C.!                                                                        n.sub.D                               __________________________________________________________________________    4.312   SCH.sub.2 CO.sub.2 Et           1.53242 (20.2° C.)             4.313   SCH.sub.3                                                             4.314   SEt                                                                   4.315   Sprop                                                                 4.316                                                                                  ##STR179##                                                           4.317   S nbutyl                                                              4.318                                                                                  ##STR180##                                                           4.319                                                                                  ##STR181##                                                           4.320   OCH.sub.3                                                             4.321   OEt                                                                   4.322   O prop                                                                4.323                                                                                  ##STR182##                                                           4.324   O nbutyl                                                              4.325                                                                                  ##STR183##                                                           4.326                                                                                  ##STR184##                                                           4.327                                                                                  ##STR185##                                                           4.328                                                                                  ##STR186##                                                           4.329                                                                                  ##STR187##                                                           4.330                                                                                  ##STR188##                                                           4.331                                                                                  ##STR189##                                                           4.332                                                                                  ##STR190##                                                           4.333                                                                                  ##STR191##                                                           4.334                                                                                  ##STR192##                                                           4.335                                                                                  ##STR193##                                                           4.336                                                                                  ##STR194##                                                           4.337                                                                                  ##STR195##                                                           4.338                                                                                  ##STR196##                                                           4.339                                                                                  ##STR197##                                                           4.340                                                                                  ##STR198##                                                           4.341                                                                                  ##STR199##                                                           4.342                                                                                  ##STR200##                                                           4.343                                                                                  ##STR201##           98-100                                          4.344                                                                                  ##STR202##           103-105                                         4.345                                                                                  ##STR203##           93-96                                           4.346                                                                                  ##STR204##                                                           4.347                                                                                  ##STR205##                     1.51180                               4.348                                                                                  ##STR206##           101-103                                         4.349                                                                                  ##STR207##           105-108                                         4.350                                                                                  ##STR208##           96-98                                           4.351                                                                                  ##STR209##                                                           4.352                                                                                  ##STR210##                                                           4.353                                                                                  ##STR211##                                                           4.354                                                                                  ##STR212##                                                           __________________________________________________________________________    General formula                                                                ##STR213##                                                                   Example                         Physical Constant                             No.     R.sup.5                                                                             R.sup.6           mp:  °C.!                                                                       n.sub.D                              __________________________________________________________________________    4.355   CN    N(C.sub.2 H.sub.5).sub.2                                                                        89-90                                         4.356   CN                                                                                   ##STR214##       123-124                                       4.357   CN    CH.sub.3                                                        4.358   CN    CH.sub.2 OCH.sub.3                                              4.359   CN    Br                                                              4.360   CN    Cl                                                              4.361   CN    OCH.sub.2 CH.sub.2 OCH.sub.3                                    4.362   NO.sub.2                                                                             ##STR215##                                                     __________________________________________________________________________

The following examples illustrate the possibilities for use of thecompounds of the invention.

In these Examples, herbicidal activity is denoted on a score of 0 to 4in which:

0=no damage

1=1-24% damage

2=25-74% damage

3=75-89% damage

4=90-100% damage

The abbreviations used for the various plant species have the followingmeanings

ABUTH=Abutilon theophrasti VERPE=Veronica persica

AGRRE=Elymus repens VIOSS=Viola sp

ALOMY=Alopecurus myosuroides

AVEFA=Avena fatua

BROTE=Bromus tectorum

CYPDI=Cyperus difformis

CYPES=Cyperus esculentus

ECHGH=Echinochloa crus-galli

GALAP=Galium aparine

GOSHI=Gossypium hirsutum

IPOSS=Ipomea purpurea

MATCH=Matricaria chamomilla

MOOVA=Monochoria vaginalis

ORYSA=Oryza sativa

PANSS=Panicum maximum

PASDS=Paspalum distichum

POLSS=Polygonum sp.

SCPJU=Scirpus juncoides

SEBEX=Sesbania exaltata

SETVI=Setaria viridis

SORHA=Sorghum halepense

SOLSS=Solanum sp.

TEST EXAMPLE A

In a greenhouse, the noted plant species were treated pre-emergentlywith the noted compounds, at a rate of 0.1 kg active ingredient/ha. Thecompounds were sprayed evenly over the soil as emulsions in 500 litreswater/ha. Three weeks after the treatment, the compounds of theinvention showed excellent activity against the weeds. The comparisonmaterial did not show the same high activity.

    __________________________________________________________________________              Compounds                                                                     A A A B S   P S C   A I M P S S V V                                           L G V R E   A O Y   B P A O E O E I                                           O R E O T   N R P   U O T L B L R O                                           M R F T V   S H E   T S C S E S P S                                           Y E A E I   S A S   H S H S X S E S                                 __________________________________________________________________________    Ex. 1.1   --                                                                              --                                                                              --                                                                              --                                                                              3   3 3 --  3 --                                                                              4 2 1 4 3 4                                 Ex. 1.2   3 --                                                                              3 --                                                                              4   4 --                                                                              --  4 3 4 4 4 4 4 4                                 Ex, 1.6   3 3 3 --                                                                              4   4 3 --  4 --                                                                              4 4 3 4 4 4                                 Ex, 1.7   --                                                                              --                                                                              --                                                                              --                                                                              3   3 3 --  4 --                                                                              4 3 4 4 4 2                                 Ex, 1.8   2 --                                                                              --                                                                              --                                                                              2   2 3 --  4 --                                                                              4 4 3 4 3 2                                 Ex, 1.9   2 2 3 --                                                                              4   3 3 --  4 --                                                                              4 3 3 4 4 4                                 Ex, 1.11  2 --                                                                              3 --                                                                              4   3 3 --  3 --                                                                              4 1 0 4 4 3                                 Ex, 1.13  3 --                                                                              3 --                                                                              4   3 4 2   4 --                                                                              4 4 3 4 4 2                                 Ex. 1.15  3 2 2 --                                                                              4   4 2 --  --                                                                              --                                                                              4 2 2 4 3 4                                 Ex, 1.18  4 3 3 --                                                                              4   4 4 3   4 --                                                                              4 4 2 4 4 4                                 Ex, 2.1   3 4 4 4 4   4 4 3   4 4 4 4 4 4 4 4                                 Ex, 2.11  3 --                                                                              3 --                                                                              --  4 4 4   3 4 4 4 4 4 4 4                                 Ex. 2.12  3 --                                                                              3 --                                                                              4   4 4 --  4 3 4 4 4 4 4 4                                 Ex, 2.13  3 --                                                                              --                                                                              --                                                                              4   4 4 --  3 3 4 4 4 3 4 4                                 Ex, 2.17  3 3 3 --                                                                              4   4 4 --  4 4 4 4 4 4 4 4                                 Ex, 2.18  3 --                                                                              3 --                                                                              4   4 3 --  4 --                                                                              4 4 2 4 4 4                                 Ex. 2.24  3 --                                                                              3 --                                                                              3   3 3 3   4 4 3 4 4 4 4 3                                 Ex, 2.38  3 --                                                                              --                                                                              --                                                                              3   3 --                                                                              --  4 3 4 3 4 4 4 4                                 Ex. 4.12  4 4 4 3 4 4 4 3 4 4 4 4 4 4 4 4 4 4                                 Untreated 0 0 0 0 0   0 0 0   0 0 0 0 0 0 0 0                                 Comparison                                                                    5-tert-butyl-3-                                                                         0 0 0 1 2   4 0 0   1 1 3 1 0 3 2 3                                 (2,4-dichloro-5-                                                              isopropoxyphenyl)--                                                           1,3,4-oxadiazol-2-one                                                         __________________________________________________________________________

TEST EXAMPLE B

In a greenhouse, the noted plant species were treated post-emergentlywith the noted compounds, at a rate of 0.3 kg active ingredient/ha. Thecompounds were sprayed evenly over the plants as emulsions in 500 litreswater/ha. Two weeks after the treatment, the compounds of the inventionshowed activity against the weeds. The comparison material did not showthe same high activity.

    __________________________________________________________________________              Compounds                                                                     A A A B S P S C A G I M P S S V V                                             L G V R E A O Y B A P A O E O E I                                             O R E O T N R P U L O T L B L R O                                             M R F T V S H E T A S C S E S P S                                             Y E A E I S A S H P S H S X S E S                                   __________________________________________________________________________    Ex. 1.0   2 2 2 --                                                                              4 3 3 --                                                                              4 3 4 4 4 4 4 4 3                                   Ex. 1.1   3 3 3 --                                                                              4 3 3 --                                                                              4 3 3 4 4 4 4 4 3                                   Ex. 1.2   4 --                                                                              3 --                                                                              3 --                                                                              3 3 4 3 4 4 4 4 4 4 4                                   Ex, 1.6   4 3 3 2 4 3 3 3 4 3 4 4 4 4 4 4 4                                   Ex. 1.7   3 3 2 --                                                                              3 3 3 --                                                                              4 4 4 3 4 4 4 4 4                                   Ex, 1.8   3 3 3 --                                                                              3 3 3 3 4 3 4 3 4 4 4 4 4                                   Ex, 1.10  --                                                                              --                                                                              3 --                                                                              3 --                                                                              3 --                                                                              4 --                                                                              3 3 4 3 4 4 3                                   Ex, 1.12  --                                                                              --                                                                              --                                                                              --                                                                              3 2 3 --                                                                              4 --                                                                              3 2 4 3 4 3 3                                   Ex. 1.13  3 2 3 --                                                                              3 3 3 3 4 --                                                                              4 4 4 3 4 4 3                                   Ex. 1.18  3 3 3 3 4 3 3 3 4 4 4 4 4 4 4 4 3                                   Ex. 2.1   3 3 4 4 4 4 3 4 4 4 4 4 4 4 4 4 4                                   Ex, 2.11  3 3 3 --                                                                              4 4 4 --                                                                              4 4 4 4 4 4 4 4 4                                   Ex. 2.12  3 --                                                                              4 --                                                                              3 3 4 3 4 4 3 4 4 4 4 4 3                                   Ex. 2.13  3 --                                                                              3 --                                                                              3 --                                                                              3 3 4 3 4 4 4 4 4 4 3                                   Ex. 2.17  3 3 3 --                                                                              4 3 3 3 4 3 4 4 4 4 4 4 3                                   Ex. 2.18  3 --                                                                              3 --                                                                              3 3 3 3 4 3 3 4 4 4 4 4 3                                   Ex. 2.24  3 --                                                                              3 --                                                                              3 3 3 3 4 3 4 3 4 4 4 4 3                                   Ex. 2.38  --                                                                              3 --                                                                              --                                                                              3 3 --                                                                              --                                                                              4 3 3 4 3 4 4 4 4                                   Ex. 4.12  4 3 4 4 4 4 3 3 4 4 4 4 4 4 4 4 4                                   Untreated 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   Comparison                                                                              0 1 1 0 1 0 1 1 4 2 3 2 3 2 4 1 3                                   5-tert-butyl-3-                                                               (2,4-dichloro-5-                                                              isopropoxyphenyl)-                                                            1,3,4-oxadiazol-2-one                                                         __________________________________________________________________________

TEST EXAMPLE C

In a greenhouse, the compounds noted in the table were applied at therates mentioned. For this the formulated active ingredients werepipetted onto the water surface

The test plants were treated pre-emergently and in the 1-3 leaf stage.

    ______________________________________                                                Concen-                                                                       tration                                                               Compound                                                                              kg/ha   ORYSA   ECHCO CYPDI SCPJU MOOVA                               ______________________________________                                        Ex. 1.0 0.04    0       2     4     1     4                                   Ex. 1.1 0.04    0       3     4     3     4                                   Ex. 1.17                                                                              0.1     0       --    4     --    4                                   Ex. 1.2 0.005   1       4     4     4     4                                   Ex. 1.4 0.05    1       3     4     2     4                                   Ex. 1.5 0.10    0       3     4     1     2                                   Ex. 1.6 0.04    1       4     4     4     4                                   Ex. 1.7 0.04    0       4     4     3     2                                   Ex. 1.8 0.04    0       4     4     4     4                                   Ex. 1.9 0.0125  0       3     4     3     4                                   Ex. 1.10                                                                              0.01    0       4     4     4     4                                   Ex. 1.11                                                                              0.05    1       4     4     4     4                                   Ex. 1.13                                                                              0.02    1       3     4     2     4                                   Ex. 1.14                                                                              0.02    0       4     4     2     4                                   Ex. 1.15                                                                              0.01    0       1     4     0     4                                   Ex. 1.18                                                                              0.01    2       4     4     3     4                                   Ex. 1.21                                                                              0.025   1       4     4     3     4                                   Ex. 1.22                                                                              0.05    1       4     4     2     4                                   Ex. 1.29                                                                              0.2     0       --    4     3     4                                   Ex. 1.36                                                                              0.04    1       4     4     3     4                                   Ex. 2.0 0.05    1       3     4     3     4                                   Ex. 2.1 0.01    1       4     4     4     4                                   Ex. 2.17                                                                              0.01    0       3     --    1     4                                   Ex. 2.18                                                                              0.01    1       3     4     2     4                                   Ex. 2.38                                                                              0.04    0       3     --    2     4                                   Ex. 3.3 0.08    1       4     4     4     4                                   Ex. 4.100                                                                             0.05    1       4     4     4     4                                   Ex. 4.101                                                                             0.05    1       4     3     3     4                                   Ex. 4.102                                                                             0.025   0       --    4     --    4                                   Ex. 4.103                                                                             0.01    0       --    --    --    4                                   Ex. 4.104                                                                             0.1     1       4     4     3     4                                   Ex. 4.105                                                                             0.05    1       4     4     4     4                                   Ex. 4.122                                                                             0.04    1       --    --    --    4                                   Ex. 4.125                                                                             0.025   0       4     4     4     4                                   Ex. 4.129                                                                             0.1     0       4     4     3     4                                   Ex. 4.130                                                                             0.025   1       4     4     3     4                                   Ex. 4.135                                                                             0.025   1       3     4     3     4                                   Ex. 4.137                                                                             0.1     0       3     --    --    4                                   Ex. 4.138                                                                             0.04    0       --    4     2     3                                   Ex. 4.140                                                                             0.04    0       4     4     3     4                                   Ex. 4.141                                                                             0.08    0       3     4     3     4                                   Ex. 4.143                                                                             0.08    0       3     4     3     4                                   Ex. 4.144                                                                             0.04    0       --    4     --    4                                   Ex. 4.146                                                                             0.2     0       4     4     3     4                                   Ex. 4.147                                                                             0.08    0       4     4     2     4                                   Ex. 4.148                                                                             0.08    0       4     4     2     4                                   Ex. 4.150                                                                             0.04    0       4     4     --    4                                   Ex. 4.151                                                                             0.04    0       --    4     --    3                                   Ex. 4.152                                                                             0.1     0       4     3     4     4                                   Ex. 4.153                                                                             0.1     0       4     4     3     4                                   Ex. 4.154                                                                             0.04    0       4     4     2     4                                   Ex. 4.155                                                                             0.04    1       4     4     2     4                                   Ex. 4.157                                                                             0.2     0       4     3     3     4                                   Ex. 4.158                                                                             0.1     0       4     4     4     4                                   Ex. 4.159                                                                             0.1     0       4     4     4     4                                   Ex. 4.164                                                                             0.05    0       4     4     4     4                                   Ex. 4.165                                                                             0.05    0       4     4     4     4                                   Ex. 4.166                                                                             0.05    1       4     4     4     4                                   Ex. 4.167                                                                             0.05    0       4     4     3     4                                   Ex. 4.168                                                                             0.05    0       4     4     3     4                                   Ex. 4.169                                                                             0.05    0       4     4     3     4                                   Ex. 4.177                                                                             0.08    0       4     4     4     4                                   Ex. 4.178                                                                             0.025   0       4     4     4     4                                   Ex. 4.179                                                                             0.1     1       3     4     3     4                                   Ex. 4.180                                                                             0.05    1       4     4     3     4                                   Ex. 4.185                                                                             0.1     1       3     4     2     4                                   Ex. 4.186                                                                             0.1     1       4     --    2     4                                   Ex. 4.187                                                                             0.005   --      3     3     2     3                                   Ex. 4.189                                                                             0.005   1       3     4     3     3                                   Ex. 4.191                                                                             0.02    1       4     4     --    4                                   Ex. 4.192                                                                             0.04    0       --    4     --    3                                   Ex. 4.194                                                                             0.05    1       --    --    3     4                                   Ex. 4.196                                                                             0.1     1       4     3     4     4                                   Ex. 4.197                                                                             0.1     1       4     4     4     4                                   Ex. 4.198                                                                             0.1     0       3     --    --    4                                   Ex. 4.2 0.025   0       4     --    4     4                                   Ex. 4.200                                                                             0.01    1       3     --    --    4                                   Ex. 4.205                                                                             0.025   1       4     --    4     4                                   Ex. 4.206                                                                             0.04    0       3     4     2     4                                   Ex. 4.228                                                                             0.08    0       4     4     3     4                                   Ex. 4.230                                                                             0.08    1       3     4     2     4                                   Ex. 4.234                                                                             0.04    0       4     4     3     4                                   Ex. 4.26                                                                              0.025   0       4     4     3     4                                   Ex. 4.27                                                                              0.01    1       4     4     2     4                                   Ex. 4.227                                                                             0.1     1       3     2     3     4                                   Ex. 4.229                                                                             0.05    1       4     --    4     4                                   Ex. 4.231                                                                             0.1     0       3     --    --    4                                   Ex. 4.233                                                                             0.08    0       4     4     3     4                                   Ex. 4.235                                                                             0.02    1       3     4     --    4                                   Ex. 4.236                                                                             0.2     0       4     4     2     4                                   Ex. 4.237                                                                             0.04    0       3     4     3     4                                   Ex. 4.238                                                                             0.04    0       4     4     3     4                                   Ex. 4.239                                                                             0.04    0       4     4     4     4                                   Ex. 4.240                                                                             0.08    1       3     4     2     4                                   Ex. 4.241                                                                             0.04    0       3     4     2     4                                   Ex. 4.242                                                                             0.04    0       --    4     --    3                                   Ex. 4.243                                                                             0.08    0       2     4     2     4                                   Ex. 4.244                                                                             0.08    0       4     4     3     4                                   Ex. 4.245                                                                             0.08    0       3     4     2     4                                   Ex. 4.246                                                                             0.1     0       4     4     --    4                                   Ex. 4.247                                                                             0.1     0       4     4     3     4                                   Ex. 4.248                                                                             0.025   0       3     4     2     4                                   Ex. 4.25                                                                              0.05    1       4     4     3     4                                   Ex. 4.251                                                                             0.1     1       3     --    4     4                                   Ex. 4.252                                                                             0.05    0       --    3     --    --                                  Ex. 4.255                                                                             0.1     0       --    --    --    4                                   Ex. 4.257                                                                             0.1     0       3     3     --    4                                   Ex. 4.275                                                                             0.025   0       4     --    3     4                                   Ex. 4.276                                                                             0.005   1       4     4     3     4                                   Ex. 4.277                                                                             0.005   1       --    3     --    3                                   Ex. 4.280                                                                             0.1     1       --    3     --    4                                   Ex. 4.281                                                                             0.025   1       3     --    2     4                                   Ex. 4.288                                                                             0.2     0       --    4     --    4                                   Ex. 4.29                                                                              0.05    1       4     4     4     4                                   Ex. 4.290                                                                             0.1     0       3     4     2     4                                   Ex. 4.291                                                                             0.025   1       4     4     3     4                                   Ex. 4.292                                                                             0.1     0       4     4     3     4                                   Ex. 4.295                                                                             0.2     0       3     --    4     4                                   Ex. 4.31                                                                              0.1     0       3     4     3     4                                   Ex. 4.32                                                                              0.005   1       3     4     2     4                                   Ex. 4.33                                                                              0.005   1       --    --    --    4                                   Ex. 4.34                                                                              0.002   1       3     4     2     4                                   Ex. 4.35                                                                              0.005   1       4     4     4     4                                   Ex. 4.37                                                                              0.01    0       3     2     2     4                                   Ex. 4.38                                                                              0.025   1       --    --    --    4                                   Ex. 4.41                                                                              0.005   1       3     4     --    4                                   Ex. 4.42                                                                              0.02    1       4     4     3     4                                   Ex. 4.43                                                                              0.02    1       4     3     2     4                                   Ex. 4.49                                                                              0.25    1       --    3     --    4                                   Ex. 4.50                                                                              0.02    1       3     4     2     4                                   Ex. 4.56                                                                              0.1     1       3     4     2     4                                   Ex. 4.57                                                                              0.025   1       4     --    3     4                                   Ex. 4.58                                                                              0.05    0       4     4     3     4                                   Ex. 4.59                                                                              0.04    0       4     4     4     4                                   Ex. 4.60                                                                              0.1     0       4     4     4     4                                   Ex. 4.61                                                                              0.02    0       4     4     2     4                                   Ex. 4.62                                                                              0.04    0       4     4     2     4                                   Ex. 4.64                                                                              0.04    0       4     4     2     4                                   Ex. 4.65                                                                              0.005   0       3     4     3     4                                   Ex. 4.66                                                                              0.1     0       --    --    --    4                                   Ex. 4.67                                                                              0.1     0       --    --    --    4                                   Ex. 4.68                                                                              0.04    0       4     4     2     4                                   Ex. 4.69                                                                              0.01    0       4     4     2     4                                   Ex. 4.70                                                                              0.08    0       4     4     4     4                                   Ex. 4.71                                                                              0.08    0       3     4     3     4                                   Ex. 4.73                                                                              0.05    0       4     4     4     4                                   Ex. 4.74                                                                              0.08    0       4     4     3     4                                   Ex. 4.75                                                                              0.05    0       4     4     4     4                                   Ex. 4.76                                                                              0.04    0       3     4     2     4                                   Ex. 4.79                                                                              0.04    0       3     --    --    4                                   Ex. 4.80                                                                              0.04    1       4     --    3     4                                   Ex. 4.82                                                                              0.1     0       --    --    --    4                                   Ex. 4.83                                                                              0.1     0       4     4     4     4                                   Ex. 4.84                                                                              0.02    1       3     4     3     4                                   Ex. 4.85                                                                              0.025   0       4     4     3     4                                   Ex. 4.87                                                                              0.1     0       4     4     3     4                                   Ex. 4.88                                                                              0.1     0       4     4     2     4                                   Ex. 4.89                                                                              0.1     0       --    3     --    4                                   Ex. 4.90                                                                              0.025   0       3     --    --    4                                   Ex. 4.91                                                                              0.1     0       4     4     3     4                                   Ex. 4.92                                                                              0.05    1       4     4     4     4                                   Ex. 4.93                                                                              0.025   0       4     4     2     4                                   Ex. 4.94                                                                              0.1     0       --    --    3     4                                   Ex. 4.95                                                                              0.025   1       4     3     3     4                                   Ex. 4.96                                                                              0.005   0       3     4     2     4                                   Ex. 4.97                                                                              0.1     0       4     4     4     4                                   Ex. 4.98                                                                              0.05    1       4     4     3     4                                   Ex. 4.99                                                                              0.025   1       4     4     3     4                                   Untreated       0       0     0     0     0                                   ______________________________________                                    

As the table shows, the compounds of the invention show good activityagainst Echinochloa crus-galli (ECHGH) Cyperus difformis (CYPDI),Scirpus juncoides (SCPJU) and Monochoria vaginalis (MOOVA).

EXAMPLE D

In a greenhouse, the noted plant species were treated with the notedcompounds, at a rate of 0.03 kg active ingredient/ha. The compounds weresprayed evenly over the plants as emulsions in 500 litres water/ha. Twoweeks after the treatment, the compounds of the invention showedexcellent activity against the weeds. The comparison material did notshow the same high activity.

    ______________________________________                                               Compound                                                                      A   S     P     A   G   I   M   P   S   S   V   V                             L   E     A     B   A   P   A   O   E   O   E   I                             O   T     N     U   L   O   T   L   B   L   R   O                             M   V     S     T   A   S   C   S   E   S   P   S                             Y   I     S     H   P   S   H   S   X   S   E   S                      ______________________________________                                        Ex. 3.1  3     4     4   4   3   4   4   4   4   4   4                                                     4                                                                             Untreated 0 0 0 0 0 0 0 0 0 0 0 0                                             Comparison                                                                    5-tert.-Butyl- 1 2 1 3 2 3 2 3 2 4 2 2                                        3-(2,4-dichloro                                                               isopropoxy-                                                                   phenyl)-                                                                      1,3,4-                                                                        oxadiazol-2-                                                                  one                                              ______________________________________                                    

EXAMPLE E

in a greenhouse, the noted plant species were treated with the notedcompounds, at a rate of 0.1 kg active ingredient/ha. The compounds weresprayed evenly over the plants as emulsions in 500 litres water/ha. Twoweeks after the treatment, the compounds of the invention showedexcellent activity against the weeds. The comparison material did notshow the same high activity.

    __________________________________________________________________________              Compounds                                                                     A A A B S P S C A G I M P S S V V                                             L G V R E A O Y B A P A O E O E I                                             O R E O T N R P U L O T L B L R O                                             M R F T V S H E T A S C S E S P S                                             Y E A E I S A S H P S H S X S E S                                   __________________________________________________________________________    Ex. 4.2   --                                                                              --                                                                              --                                                                              --                                                                              3 3 3 --                                                                              4 3 3 4 4 --                                                                              4 4 4                                   Ex. 4.3   3 --                                                                              3 3 4 4 3 --                                                                              4 4 4 4 4 4 4 4 3                                   Ex. 4.4   4 3 3 3 4 4 3 3 4 4 4 4 4 4 4 4 3                                   Untreated 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                   Comparison                                                                    5-tert.-Butyl-3-                                                                        1 1 0 0 2 2 1 0 4 2 3 2 3 4 3 2 2                                   (2,4-dichloro-5-                                                              isopropoxyphenyl)-                                                            1,3,4-oxadiazol-2-one                                                         __________________________________________________________________________

We claim:
 1. Substituted pyrazolyl derivative of the general formula##STR216## in which R³ is hydrogen or halogen,R⁵ is hydrogen, nitro,cyano, --COOR⁷, --C(═X)NR⁸ R⁹ or --C(═X)R₁₀, ##STR217## R⁷, R⁸ and R⁹,which may be the same or different, arc hydrogen or C₁ -C₄ -alkyl or R⁸and R⁹ together with the nitrogen to which they are attached form a 5 or6 membered saturated ring, R¹⁰ is hydrogen or C₁ -C₄ -alkyl, optionallysubstituted by one or more halogen atoms, R¹¹ is hydrogen, C₁ -C₄-alkyl, C₂ -C₆ -alkenyl, C₃ -C₆ -alkynyl or phenyl. (each of which isoptionally substituted by one or more halogen atoms), C₃ -C₈-cycloalkyl, cyanomethyl or the group R²¹ CO--, R₁₂ is C₁ -C₆ -alkyl, C₂-C₆ -alkenyl, C₃ -C₆ -alkenyl or phenyl (each of which is optionallysubstituted by one or more halogen atoms), C₃ -C₈ -cycloalkyl,cyanomethyl, C₁ -C₄ alkoxy-C₁ -C₆ -alkyl di-C₁ -C₄ -alkylamino-C₁ -C₄-alkyl, tetrahydrofurfurlymethyl, C₃ -C₆ -alkynyloxy-C₁ -C₄ -alkyl,benzyl (optionally substituted by one or more halogen, nitro, cyano, C₁-C₄ -alkyl, C₁ -C₄ -alkoxy or halo-C₁ -C₄ -alkyl-groups), --C(═X)R²¹,--(CH₂)₃ --(O)_(d) --R²⁸, --(CH₂)_(a) --O--(CH₂)_(b) --R²⁸ or--(CH₂)_(a) --X--R³⁴ or R¹¹ and R¹² together with the nitrogen to whichthey are attached form a 3, 5 or 6 membered saturated carbocyclic oraromatic ring, in which a carbon atom is optionally substituted by anoxygen atom, R¹³ is hydrogen, C₁ -C₄ -alkyl, C₂ -C₆ -alkenyl or C₃ -C₆-alkynyl; or R¹³ and R¹⁴ together form the group --(CH₂)_(p) --; R¹⁴ andR¹⁵, which may be the same or different, are C₁ -C₄ -alkyl, C₂ -C₆-alkenyl, C₃ -C₆ -alkynyl or phenyl (each of which is optionallysubstituted by one or more halogen atoms), hydrogen, C₃ -C₆ -cycloalkylor the groups --XR¹⁸ or --NR¹⁹ R²⁰ ; R¹⁸ is C₁ -C₄ -alkyl, optionallysubstituted by one or more halogens; R¹⁹ and R²⁰, which may be the sameor different, are hydrogen or C₁ -C₄ -alkyl; R²¹ is C₁ -C₄ -alkoxy-C₁-C₄ -alkyl, C₁ -C₄ -alkylthio-C₁ -C₄ -alky, phenyl (substituted by oneor more halogen, nitro, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or halo-C₁-C₄ -alkyl groups), --NR³¹ R³² or --(CH₂)_(a) --(O)_(d) --R³³, R²⁸ ishydrogen, hydroxy, halogen, C₁ -C₄ -alkyl (optionally substituted one ormore C₁ -C₄ -alkoxy groups), C₃ -C₆ -cycloalkyl (optionally interruptedby one or more oxygen atoms and optionally substituted by dimethyl,furyl, thienyl or --C(═O)R²⁹, R²⁹ is C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy,R³¹ and R³², which may be the same or different, are C₁ -C₄ -alkyl orphenyl, R³³ C₃ -C₆ -cycloalkyl (optionally interrupted by one or moreoxygen atoms and optionally substituted by dimethyl), --C(═O)R²⁹, furylor thienyl, R³⁴ is C₁ -C₄ -alkyl, a and b are 1, 2 or 3, is d is 0 or 1,m is 3 or 4 and X is oxygen or sulfur, p is 2 or
 3. 2. Substitutedpyrazolyl derivative according to claim 1 in which R³ is hydrogen,chloro or bromo.
 3. Substituted pyrazolyl derivative of the generalformula ##STR218## in which R³ is hydrogen or halogen,R⁵ is hydrogen,nitro, cyano, --COOR⁷, --C(═X)NR⁸ R⁹ or --C(═X)R¹⁰, R⁶ is --NR¹¹ R ¹²R⁷, R⁸ and R⁹, which may be the same or different, are hydrogen or C₁-C₄ -alkyl or R₈ and R⁹ together with the nitrogen to which they areattached form a 5 or 6 membered saturated ring, R¹⁰ is hydrogen or C₁-C₄ -alkyl, optionally substituted by one or more halogen atoms, R¹¹ ishydrogen, C₁ -C₄ -alkyl, C₂ -C₆ -alkenyl, C₃ -C₆ -alkynyl or phenyl(each of which is optionally substituted by one or more halogen atoms),C₃ -C₈ -cycloalkyl, cyanomethyl or the group R²¹ CO--, R¹² is C₁ -C₆-alkyl, C₂ -C₆ -alkenyl, C₃ -C₆ -alkynyl or phenyl (each of which isoptionally substituted by one or more halogen atoms), C₃ -C₈-cycloalkyl, cyanomethyl, C₁ -C₄ -alkoxy-C₁ -C₆ -alkyl, di-C₁ -C₄-alkylamino-C₁ -C₄ -alkyl, tetrahydrofurfurylmethyl, C₃ -C₆-alkynyloxy-C₁ -C₄ -alkyl, benzyl (optionally substituted by one or morehalogen, nitro, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or halo-C₁ -C₄-alkyl groups), --C(═X)R²¹, --(CH₂)_(a) --(O)_(d) --R²⁸, --(CH₂)_(a)--O--(CH₂)_(b) --R²⁸ or --(CH₂)_(a) --X--R³⁴ or R¹¹ and R¹² togetherwith the nitrogen to which they are attached form a 3, 5 or 6 memberedsaturated carbocyclic or aromatic ring, in which a carbon atom isoptionally substituted by an oxygen atom, R²¹ is C₁ -C₄ -alkoxy-C₁ -C₄-alkyl, C₁ -C₄ -alkylthio-C₁ -C₄ -alkyl, phenyl (substituted by one ormore halogen, nitro, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or halo-C₁ -C₄-alkyl groups), --NR³¹ R³² or --(CH₂)_(a) --(O)_(d) --R³³, R²⁸ ishydrogen, hydroxy, halogen, C₁ -C₄ -alkyl (optionally substituted by oneor more C₁ -C₄ -alkoxy groups), C₃ -C₆ -cycloalkyl (optionallyinterrupted by one or more oxygen atoms and optionally substituted bydimethyl), furyl, thienyl or --C(═O)R²⁹, R²⁹ is C₁ -C₄ -alkyl or C₁ -C₄-alkoxy, R³¹ and R³², which may be the same or different, are C₁ -C₄alkyl or phenyl, R³³ C₃ -C₆ -cycloalkyl (optionally interrupted by oneor more oxygen atoms and optionally substituted by dimethyl),--C(═O)R²⁹, furyl or thienyl, R³⁴ is C₁ -C₄ -alkyl, a and b are 1, 2 or3, d is 0 or 1, m is 3 or 4 and X is oxygen or sulfur.
 4. Substitutedpyrazolyl derivative according to claim 3 in which R³ is hydrogen,chloro or bromo.
 5. Substituted pyrazolyl derivative according to claim3 in which R⁵ is cyano.
 6. Substituted pyrazole derivatives according toclaim 1 in which R⁵ is CN.
 7. Substituted pyrazolyl derivative accordingto claim 2 in which R³ chloro, and cyano.
 8. Substituted pyrazolylderivative according to claim 1 in which R³ is hydrogen and R⁵ is CN. 9.Substituted pyrazolyl derivative according to claim 1 in which R⁵ isCONH₂.
 10. A herbicidal composition which comprises a compound accordingto claim 1 in admixture with an agriculturally acceptable carrier.
 11. Aherbicidal composition which comprises a compound according to claim 2in admixture with an agriculturally acceptable carrier.
 12. A herbicidalcomposition which comprises a compound according to claim 3 in admixturewith an agriculturally acceptable carrier.
 13. A herbicidal compositionwhich comprises a compound according to claim 2 in admixture with anagriculturally acceptable carrier.
 14. A herbicidal composition whichcomprises a compound according to claim 4 in admixture with anagriculturally acceptable carrier.
 15. A herbicidal composition whichcomprises a compound according to claim 5 in admixture with anagriculturally acceptable carrier.
 16. A method of combating weeds whichcomprises applying to weeds or their locus a compound according toclaim
 1. 17. A method of combating weeds which comprises applying toweeds or their locus a compound according to claim
 2. 18. A method ofcombating weeds which comprises applying to weeds or their locus acompound according to claim
 3. 19. A method of combating weeds whichcomprises applying to weeds or their locus a compound according to claim4.
 20. A method of combating weeds which comprises applying to weeds ortheir locus a compound according to claim
 5. 21. A method of combatingweeds which comprises applying to weeds or their locus a compoundaccording to claim 6.